Compositions containing microcapsules coated with deposition proteins

ABSTRACT

A microcapsule composition containing microcapsules coated with a deposition protein, e.g., a protein-silanol copolymer, a protein-silane copolymer, a protein-siloxane copolymer, or a cationically modified protein, is provided as is a method for making the microcapsule composition and using the microcapsule composition in consumer products, in particular rinse-off consumer product.

BACKGROUND

Fragrance microcapsules are efficient delivery systems that can providelasting release of fragrance in variety of applications. The challengehowever is when the intended use of the product is to clean and rinseparticles, oils and dirt, as is the case with shampoos, detergents, bodywash and hair conditioners. Therefore, there is a need in the art formicrocapsule compositions with improved deposition characteristicssuitable for rinse-off consumer product applications.

WO 2008/142637 describes a coacervated capsule, wherein the core iscomposed of a hydrophobic material, and the shell is composed of aprotein such as an albumin, vegetable globulin or gelatine, andoptionally a non-protein polymer.

WO 2009/080401 discloses capsules composed of a shell and a carrier oilcore, wherein the shell is permeable to free perfume and is composed ofan aminoplast, protein, polyurethane, polysaccharide, gum orpolymethylmethacrylate.

WO 2011/056904 provides an encapsulate containing a core, a shell havingan inner and outer surface and a coating, wherein the coating is on theouter surface of the shell and is composed of a cationic polymer, e.g.,a protein, and an anionic polymer, e.g., a protein.

WO 2012/001604 describes a coacervated capsule having a core composed ofa mixture of a fatty component and a flavor or fragrance materialencapsulated within a coating layer composed essentially of a protein,and optionally a non-protein polymer.

SUMMARY OF THE INVENTION

The present invention provides a microcapsule composition composed of aplurality of microcapsules each containing a polymeric wall and anactive material encapsulated within the polymeric wall, wherein thepolymeric wall is coated with a deposition protein. In some embodiments,the deposition protein is a cationically modified protein (e.g., aprotein-acrylate copolymer comprising at least one nitrogen-containingacrylic moiety such as a tertiary or quaternary amine group), aprotein-silanol copolymer, a protein-silane, a protein-siloxanecopolymer, or a combination thereof. In certain embodiments, thedeposition protein has the structure of Formula I or Formula II:

wherein R is a protein residue; R¹ is a protein cross-linker group; R²and R³ are each independently hydrogen, hydroxyl, halo, C₁-C₆ alkyl, orC₁-C₆ alkoxy; and n is 1 to 100. Deposition proteins of the microcapsulecomposition can include a modified vegetable protein, wheat protein,marine collagen protein, keratin protein, silk protein, or milk protein,wherein the deposition protein has a molecular weight in the range of1000 to 500,000. In some embodiments, the active material of themicrocapsule composition can include a fragrance, pro-fragrance, flavor,malodor counteractive agent, anti-inflammatory agent, anesthetic,analgesic, anti-viral agent, anti-infectious agent, anti-acne agent,skin lightening agent, insect repellant, emollient, skin moisturizingagent, vitamin or derivative thereof, nanometer to micron size inorganicsolid, polymeric or elastomeric particle, or combination thereof. Inother embodiments, the polymeric wall is composed of polyacrylate,polyurea, polyurethane, polyacrylamide, poly(acrylate-co-acrylamide),starch, silica, gelatin and gum Arabic, poly(melamine-formaldehyde),poly(urea-formaldehyde), or a combination thereof. In furtherembodiments, the microcapsule composition includes a second depositionaid.

A method for preparing the microcapsule composition of the invention isalso provided. The method involves the steps of (a) providing amicrocapsule slurry having a plurality of microcapsules each containinga polymeric wall and an active material encapsulated within thepolymeric wall; and (b) curing the microcapsules and coating each of themicrocapsules with a deposition protein. In some embodiments, themicrocapsules are coated with the deposition protein at a temperaturebetween 0 to 250° C. before, during or after curing the microcapsules.In other embodiments, the microcapsules are coated with a seconddeposition aid. In embodiments where the deposition protein is aprotein-silanol copolymer, a protein-silane copolymer, aprotein-siloxane copolymer, or a combination thereof, the microcapsulesare coated at a temperature between 35 to 75° C. before, during or aftercuring the microcapsules. In some embodiments, the deposition protein iscross-linked with a cross-linking agent, e.g., a transglutaminase oralkoxysilane.

A consumer product containing the microcapsule composition is alsoprovided, wherein said consumer product can include one or moredifferent microcapsules, free active material, or a combination thereof.Consumer products include, but are not limited to a shampoo, hairconditioner, body wash, detergent, softener, bar soap, scent booster, orhard surface cleaner.

DETAILED DESCRIPTION OF THE INVENTION

It has now been found that modified proteins serve as depositionperformance enhancers for microcapsules in various rinse-off consumerproduct applications. Without wishing to be bound by theory, it isposited that proteins may potentially improve the interactions tovarious substrates such as hair and skin.

Accordingly, this invention provides a microcapsule composition composedof a plurality of microcapsules each containing a polymeric wall and anactive material encapsulated within the polymeric wall, wherein thepolymeric wall is coated with a deposition protein. The terms “capsule”and “microcapsule” are used interchangeably. Microcapsules of thisinvention preferably have a size in the range of from 0.01 to 1000microns in diameter (e.g., 0.5 to 1000 microns, 1 to 200 microns, 0.5 to150 microns, 0.1 to 100 microns, 2 to 50 microns, 5 to 25 microns, 2 to15 microns, and 1 to 10 microns), wherein the capsule distribution canbe narrow, broad, or multi-modal.

As with conventional deposition agents, a deposition protein of thisinvention aids in deposition of microcapsules to surfaces such asfabric, hair or skin. The protein component starting material which isused in the preparation of the deposition protein may be derived fromeither animal or vegetable sources, or by fermentation. Examples ofproteins, which can be used as the protein component, include collagen,elastin, keratin, casein, or other milk protein; wheat protein;vegetable protein such as potato protein or soya protein; and/or silkprotein. Wheat protein and/or potato protein are particularly preferred,and especially wheat protein.

The term “protein” is used herein to include both native (or chemicallyunmodified) and hydrolyzed proteins, and thus includes proteins as wellas polypeptides, peptides, amino acids and/or peptones, the latter ofwhich can be categorized as hydrolyzed proteins. Hydrolyzed proteins arepreferred, particularly polypeptides and peptides, which may, forexample, be produced by acid, alkali, and/or enzyme hydrolysis, ofnative proteins. In this respect, the molecular weight (average weight)of the protein component may vary over a wide range, such as for examplein the range from 100 to 500,000 Daltons, e.g., preferably 30,000 to200,000, more preferably 50,000 to 150,000, particularly 60,000 to100,000, and especially 70,000 to 90,000 Daltons.

The composition of the amino acids in the protein component preferablyincludes at least 1%, preferably in the range from 2 to 25%, morepreferably 3 to 15%, particularly 4 to 10%, and especially 6 to 8% w/wof basic amino acids. The basic amino acids will normally be arginine,lysine, and/or histidine.

Commercially available examples of proteins of use in preparing thedeposition protein of this invention include, but are not limited to,COLLASOL (high molecular weight, soluble, marine collagen; Croda),CROPEPTIDE (hydrolyzed wheat protein and hydrolyzed wheat starch;Croda), CROSILK 10000 (hydrolyzed silk protein; Croda), CROTEIN(hydrolyzed collagen; Croda), HYDROLACTIN 2500 (hydrolyzed milk protein;Croda), HYDROSOLANUM (hydrolyzed vegetable protein; Croda), HYDROSOY2000 PE (hydrolyzed soy protein; Croda), HYDROTRITICUM 2000 PE(hydrolyzed wheat protein; Croda), KERASOL (hydrolyzed keratin; Croda),PROLEVIUM (cottonseed protein hydrolyzate; Croda), PROSINA (hydrolyzedkeratin; Croda), TRITISOL (Hydrolyzed wheat protein; Croda), FisionKeraVeg18 (wheat amino acids, soy amino acids; Tri-K), MILK-TEIN(hydrolyzed milk protein; Tri-K), Rice PRO-TEIN (hydrolyzed riceprotein; Tri-K), RICE-QUAT C (cocodimonium hydroxypropyl hydrolyzed riceprotein; Tri-K), SOY-QUAT L (laurdimonium hydroxypropyl hydrolyzed soyprotein; Tri-K), WHEAT-QUAT C (cocodimonium hydroxypropyl hydrolyzedwheat protein; Tri-K), QUINOA PRO EX (hydrolyzed quinoa; Tri-K),BARLA-TEIN Pro (hydrolyzed barley protein; Tri-K), KERA-QUAT WKP(hydrolyzed keratin; Tri-K), KERA-TEIN 1000 (hydrolyzed keratin; Tri-K),KERA-TEIN 1000 SD (hydrolyzed keratin; Tri-K), Proto-lan 8 (cocoylhydrolyzed collagen; Tri-K), Proto-lan KT (cocoyl hydrolyzed collagen;Tri-K), SILK AA-QUAT C (cocodimonium hydroxypropyl silk amino acids;Tri-K), AMINO SILK SF (silk amino acids; Tri-K), Collagen HydrolyzateCosmetic N-55 (Tri-K), FLAX-TEIN Pro (hydrolyzed linseed protein;Tri-K), SOY-TEIN NL (hydrolyzed soy protein; Tri-K), Silk PRO-TEIN(hydrolyzed silk; Tri-K), WHEAT-TEIN W (hydrolyzed wheat protein;Tri-K), and MARI-COLL N-30 (hydrolyzed collagen; Tri-K).

The deposition protein can be prepared by modifying native and/orhydrolyzed protein to include a cationic and/or silicon moiety.Accordingly, in certain embodiments, the deposition protein is acationically modified protein, a protein-silanol copolymer, aprotein-silane, a protein-siloxane copolymer, or a combination thereof.

Cationically Modified Deposition Protein.

A cationically modified deposition protein includes quaternary ammoniumprotein derivatives as well as protein-acrylate copolymers having anitrogen-containing acrylic moiety.

Quaternary ammonium protein derivatives can be prepared from proteinhydrolyzates in a two-step reaction using chloracetyl chloride to forman acetyl linking agent on the protein and subsequent reaction with afatty tertiary amine to form a quaternary ammonium salt of polypeptide.See, e.g., FR 1149161. A quaternary ammonium protein derivative can alsobe prepared using a 2-hydroxy-1,3-propylene linking group between theprotein hydrolysate radical and the quaternerized amino group. See JP7908688 and JP 7908728. Alternatively, a lipophilic tertiary amine canbe reacted with an epihalohydrin in the presence of water andsubsequently reacted with an aqueous hydrolyzed protein to form acationic quaternary ammonium protein derivative. See, e.g., EP 0109074.

A protein-acrylate copolymer can be produced by reacting protein withone or more of acrylic monomers, preferably by free radicalpolymerization as known in the art. Alternatively, oligomeric- and/orpolyacrylates may be reacted with the protein, for example by convertingsome of the amine groups in the polyacrylate into protected thiols usingN-succinimidyl 3-(2-pyridyldithio)propionate (SPDP). Followingdeprotection, the thiolated acrylate polymer can be conjugated to theprotein via disulphide or thioether linkages.

Protein-acrylate copolymers may be produced by reacting protein withquaternary acrylic monomers, oligomers and/or polymers, or alternativelyquaternization can occur in situ, for example by reacting protein withtertiary amine acrylic monomers, oligomers and/or polymers andquaternizing in situ for example with diethyl sulphate (e.g., in aqueoussolution), dimethyl sulphate (e.g., in DMF), or alkyl and aryl halidessuch as methyl chloride, methyl iodide, methyl bromide, ethyl chloride,and benzyl chloride. See, e.g., US 2013/0004450.

The acrylate component of the protein-acrylate copolymer may be formedfrom, or include the reaction product of, at least one nitrogencontaining acrylic monomer. The monomer may include more than onenitrogen atom, but generally will include only one nitrogen atom. Thenitrogen atom(s) is preferably part of an amine group. The amine groupmay be a primary, secondary, tertiary, and/or quaternary group.Preferably the amine group is a tertiary or quaternary, and particularlya quaternary amine group. Acrylic monomer, oligomer, and/or polymer maybe reacted with the protein component in order to form theprotein-acrylate copolymer. Quaternary acrylic monomer, oligomer, and/orpolymer may be reacted with the protein component, or alternativelyamine groups present in the copolymer may be quaternized in situ, i.e.,after reaction of the protein component with the acrylate component.

The nitrogen containing acrylic monomer can be (meth)acrylamide, amono-, di- or tri-(C₁-C₄)alkylamino (C₁-C₄)alkyl(meth)acrylate, a mono-,di- or tri-(C₁-C₄) alkylamino(C₁-C₄)alkyl(meth)acrylamide, and mixturesthereof. In certain embodiments, the acrylic monomer is adialkylaminoalkyl (meth)acrylate, a quaternized dialkylaminoalkyl(meth)acrylate, an acid addition salt of a quaternized dialkylaminoalkyl(meth)acrylate, or mixtures thereof. More preferably, the acrylicmonomer is N,N-dimethylamino ethyl methacrylate (DMAEMA),N,N-diethylamino ethyl acrylate, N,N-diethylamino ethyl methacrylate,N-t-butylamino ethyl acrylate, N-t-butylamino ethyl methacrylate,N,N-dimethylamino propyl acrylamide, N,N-dimethylamino propylmethacrylamide, N,N-diethylamino propyl acrylamide, N,N-diethylaminopropyl methacrylamide, N,N,N-trimethylamino ethyl methacrylate(DMAEMA-MC), N,N,N-triethylamino ethyl acrylate, N,N,N-triethylaminoethyl methacrylate, N,N,N-trimethylamino propyl acrylamide,N,N,N-trimethylamino propyl methacrylamide, N,N,N-triethylamino propylacrylamide, N,N,N-triethylamino propyl methacrylamide, or mixturesthereof.

Desirably at least 20, preferably at least 40, more preferably at least60, particularly in the range from 80 to 100, and especially 90 to 100mole % of the acrylic monomers include tertiary and/or quaternary,preferably quaternary, amine groups.

In addition to a nitrogen containing acrylic monomer, the acryliccomponent of the protein-acrylate copolymer can include one or moreother acrylic monomers, e.g., acrylic acid and/or methacrylic acid,and/or esters thereof, especially an alkyl ester wherein the alkyl groupcontains up to 10, more preferably up to 6, carbon atoms. Suitable alkylgroups may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, terbutyl, hexyl, 2-ethyl, hexyl, heptyl, and n-octyl. In oneembodiment, mixtures of any two or more of the aforementioned monomersare employed, for example an alkyl acrylate (such as ethyl acrylateand/or butyl acrylate) in combination with an alkyl methacrylate (suchas methyl methacrylate).

The acrylate component may also include other, preferably optional,additional monomers, in addition to the aforementioned acrylic acid ormethacrylic acid or esters thereof. Suitable additional monomersinclude, e.g., acrylonitrile, methacrylonitrile, halo-substitutedacrylonitrile, halo-substituted methacrylonitrile, hydroxyethylmethacrylate, glycidyl acrylate, glycidyl methacrylate, itaconic acid,itaconic anhydride, and half esters of itaconic acid.

The protein-acrylate copolymer may be a random, graft, or blockcopolymer. The copolymer is preferably a graft or block copolymer, andmore preferably a graft copolymer. The protein-acrylate copolymer may berepresented schematically as follows:

-   -   protein chain-X-polyacrylate        wherein X is a linking group resulting from the reaction of the        protein with the (poly)acrylate, and the part derived from the        protein is preferably NH or S, particularly NH, wherein the        polyacrylate contains between 2 to 1000, 5 to 500, 10 to 200, or        20 to 100 acrylic monomers.

Commercially available examples of cationically modified depositionproteins include, but are not limited to, CROMOIST WQ (quaternized wheatprotein; commercially available from Croda), CROQUAT WKP (quaternizedhydrolyzed keratin; Croda), CROSILQUAT (silk protein hydrolyzatequaternized by ammonium chloride cocoyldimethylammonium; Croda), andVoluminis (ethyltrimonium chloride methacrylate/hydrolyzed wheat proteincopolymer; Croda).

Protein-Silicon Copolymer Deposition Aid.

Preferred protein-silicon copolymers are those wherein the copolymer isthe reaction product of a protein hydrolyzate and an organofunctionalsilane. More preferably, the organofunctional silane includes anepoxysilane capable of reacting with one or more amino groups of theprotein, such as glycidoxypropyltrimethoxysilane. Exemplaryprotein-silicon copolymers include protein-silanol (—Si—OH),protein-silane (—Si—H), protein-siloxane (—Si—OR), and combinationsthereof.

The protein of the protein-silicon copolymer may be a native protein ora chemically modified protein (for example, quaternized) provided thatsome free amino groups are still present in the protein molecules. Theorganofunctional silane used for reaction with the protein component toform the copolymer must contain a functional group capable of reactingwith the chain terminal and/or side chain amino groups of the protein.Suitable reactive groups include, for example, acyl halide, sulphonylhalide, anhydride, aldehyde and epoxide groups. The silicon component ofthe copolymer may be any compound which contains a siloxane group(Si—O—Si) or any silane capable of forming a siloxane in situ bycondensation of silanol (Si—OH) groups (Scheme 1) or any alkoxysilane orhalosilane which hydrolyses to form a corresponding silanol (Scheme 2)and then condenses to form a siloxane group (Scheme 1).

The silicone reactant is preferably capable of forming cross-links withthe protein component. Cross-linking may be effected either through theuse of polyfunctional silicone reactants or of monofunctional siliconereactants containing silanol groups (or alkoxysilane or halosilanegroups convertible to silanol groups by hydrolysis) capable of formingsiloxane cross-links by condensation between different chains. Suchmonofunctional silicone reactants should therefore have at least one andup to three hydroxy groups attached to at least one silicon atom intheir structure.

A suitable method for the manufacture of copolymer compositions includeheating the protein component and adjusting the pH to alkaline todeprotonate the amino groups. A calculated quantity of silane (based onthe Formol titer, a technique described by Cobbett, et al. (1964) J.Appl. Chem. (London) 14:296-302) to estimate the degree of modificationof amino groups in proteins) is then added, wherein the amount of silaneis calculated to modify 5-40%, preferably 10-40% of the available aminogroups. Following reaction, the pH is adjusted to acidic, and worked upin a conventional manner. See, e.g., U.S. Pat. No. 8,048,846.

Depending on the starting material, the protein-silicon copolymer usedas a deposition protein of this invention has the structure of Formula Ior Formula II:

wherein R is a residue of a protein; R¹ is a protein cross-linker group;R² and R³ are each independently hydrogen, hydroxyl, halo, C₁-C₆ alkyl,or C₁-C₆ alkoxy; and n is 1 to 100.

“Halogen” or “halo” means fluorine, chlorine, bromine, or iodine.

“Alkyl” means a linear saturated monovalent hydrocarbon radical of oneto six carbon (i.e., C₁-C₆) atoms, e.g., methyl, ethyl, propyl,2-propyl, butyl (including all isomeric forms), or pentyl (including allisomeric forms), and the like.

“Alkoxy” means a radical —OR where R is alkyl as defined herein, e.g.,methoxy, ethoxy, propoxy, or 2-propoxy, n-, iso-, or tert-butoxy, andthe like.

Commercially available examples of protein-silanol copolymers,protein-silane copolymers, and protein-siloxane copolymers include, butare not limited to, CRODASONE W (hydrolyzed wheat protein PG-propylsilanetriol; Croda), CRODASONE P (hydrolyzed pea protein PG-propylsilanetriol; Croda), CRODASONE W (hydrolyzed wheat protein PG-propylsilanetriol; Croda), and KERAVIS (hydrolyzed vegetable protein PG-propylsilanetriol; Croda).

Core-Shell Encapsulation Systems.

Encapsulation of active material such as fragrances is known in the art,see for example, U.S. Pat. No. 2,800,457, U.S. Pat. No. 3,870,542, U.S.Pat. No. 3,516,941, U.S. Pat. No. 3,415,758, U.S. Pat. No. 3,041,288,U.S. Pat. No. 5,112,688, U.S. Pat. No. 6,329,057, and U.S. Pat. No.6,261,483. Wall forming polymers of use in this invention includepolyurethane, polysiloxanes, polyurea, polyamide, polyimide, polyvinylalcohol, polyanhydride, polyolefin, polysulfone, polysaccharide,protein, polylactide (PLA), polyglycolide (PGA), polyorthoester,polyphosphazene, silicone, lipid, modified cellulose, gums, polystyrene,and polyesters or combinations of these materials. Other polymeric wallmaterials that are functional are ethylene maleic anhydride copolymer,styrene maleic anhydride copolymer, ethylene vinyl acetate copolymer,and lactide glycolide copolymer. Biopolymers that are derived fromalginate, chitosan, collagen, dextran, gelatin, gum Arabic, silk andstarch can also be used as the encapsulating materials. Additionally,capsules can be made via the simple or complex coacervation of gelatin.Preferred encapsulating polymeric wall materials include those formedfrom urea-formaldehyde, melamine-formaldehyde phenolic-formaldehyde,urea-glutaraldehyde, melamine-glutaraldehyde, phenolic-glutaraldehyde,and combinations of these wall materials; polyurea (isocyanate-based),polyurethane, and combinations of these wall materials; acrylate-basedhydrogels; polyurea/polyurethane-acrylic hybrid materials; polyamide andpolyester-based materials; capsules produced using epoxy-basedcross-linkers; silk fibroin microcapsules, and capsules based on silicaand silica-derived materials which are typically produced using sol-gelprocesses.

Urea-Formaldehyde and Melamine-Formaldehyde Microcapsules.

Urea-formaldehyde and melamine-formaldehyde pre-condensate capsule shellwall precursors are prepared by means of reacting urea or melamine withformaldehyde where the mole ratio of melamine or urea to formaldehyde isin the range of from about 10:1 to about 1:6, preferably from about 1:2to about 1:5. For purposes of practicing this invention, the resultingmaterial has a molecular weight in the range of from 156 to 3000. Theresulting material may be used ‘as-is’ as a cross-linking agent for theaforementioned substituted or un-substituted acrylic acid polymer orcopolymer or it may be further reacted with a C₁-C₆ alkanol, e.g.,methanol, ethanol, 2-propanol, 3-propanol, 1-butanol, 1-pentanol or1-hexanol, thereby forming a partial ether where the mole ratio ofmelamine/urea:formaldehyde:alkanol is in the range of 1:(0.1-6):(0.1-6).The resulting ether moiety-containing product may be used ‘as-is’ as across-linking agent for the aforementioned substituted or un-substitutedacrylic acid polymer or copolymer, or it may be self-condensed to formdimers, trimers and/or tetramers which may also be used as cross-linkingagents for the aforementioned substituted or un-substituted acrylic acidpolymers or co-polymers. Methods for formation of suchmelamine-formaldehyde and urea-formaldehyde pre-condensates are setforth in U.S. Pat. No. 3,516,846 and U.S. Pat. No. 6,261,483, and Lee,et al. (2002) J. Microencapsulation 19:559-569.

Examples of urea-formaldehyde pre-condensates useful in the practice ofthis invention are URAC 180 and URAC 186, trademarks of Cytec TechnologyCorp. of Wilmington, Del. Examples of melamine-formaldehydepre-condensates useful in the practice if this invention, include, butare not limited to, CYMEL U-60, CYMEL U-64 and CYMEL U-65, trademarks ofCytec Technology Corp. of Wilmington, Del. It is preferable to use, asthe precondensate for cross-linking, the substituted or un-substitutedacrylic acid polymer or co-polymer. In practicing this invention, therange of mole ratios of urea-formaldehydeprecondensate/melamine-formaldehyde pre-condensate tosubstituted/un-substituted acrylic acid polymer/co-polymer is in therange of from about 9:1 to about 1:9, preferably from about 5:1 to about1:5 and most preferably from about 2:1 to about 1:2.

In one embodiment of the invention, microcapsules with polymer(s)composed of primary and/or secondary amine reactive groups or mixturesthereof and cross-linkers can also be used. See US 2006/0248665. Theamine polymers can possess primary and/or secondary aminefunctionalities and can be of either natural or synthetic origin.Amine-containing polymers of natural origin are typically proteins suchas gelatin and albumen, as well as some polysaccharides. Synthetic aminepolymers include various degrees of hydrolyzed polyvinyl formamides,polyvinylamines, polyallyl amines and other synthetic polymers withprimary and secondary amine pendants. Examples of suitable aminepolymers are the LUPAMIN series of polyvinyl formamides available fromBASF. The molecular weights of these materials can range from 10,000 to1,000,000.

Urea-formaldehyde or melamine-formaldehyde capsules can also includeformaldehyde scavengers, which are capable of binding free formaldehyde.When the capsules are for use in aqueous media, formaldehyde scavengerssuch as sodium sulfite, melamine, glycine, and carbohydrazine aresuitable. When the capsules are aimed to be used in products having lowpH, e.g., fabric care conditioners, formaldehyde scavengers arepreferably selected from beta diketones, such as beta-ketoesters, orfrom 1,3-diols, such as propylene glycol. Preferred beta-ketoestersinclude alkyl-malonates, alkyl aceto acetates and polyvinyl alcoholaceto acetates.

Polyurea (Isocyanate-Based) and Polyurethane Microcapsules.

Suitable polyurea or polyurethane microcapsules are prepared using oneor more polyisocyanates and one or more cross-linker agents.

A polyisocyanate is a molecule having two or more isocyanate groups,i.e., O═C═N—, wherein said polyisocyanate can be aromatic, aliphatic,linear, branched, or cyclic. In certain embodiments, the polyisocyanatecontains, on average, 2 to 4 —N═C═O groups. In particular embodiments,the polyisocyanate contains at least three isocyanate functional groups.In certain embodiments, the polyisocyanate is water-insoluble.

The polyisocyanate can be an aromatic or aliphatic polyisocyanate.Desirable aromatic polyisocyanates each have a phenyl, tolyl, xylyl,naphthyl or diphenyl moiety as the aromatic component. In certainembodiments, the aromatic polyisocyanate is a polymeric methylenediphenyl diisocyanate (“PMDI”), a polyisocyanurate of toluenediisocyanate, a trimethylol propane-adduct of toluene diisocyanate or atrimethylol propane-adduct of xylylene diisocyanate.

Suitable aliphatic polyisocyanates include trimers of hexamethylenediisocyanate, trimers of isophorone diisocyanate or biurets ofhexamethylene diisocyanate. Additional examples include thosecommercially available, e.g., BAYHYDUR N304 and BAYHYDUR N305, which arealiphatic water-dispersible polyisocyanates based on hexamethylenediisocyanate; DESMODUR N3600, DESMODUR N3700, and DESMODUR N3900, whichare low viscosity, polyfunctional aliphatic polyisocyanates based onhexamethylene diisocyanate; and DESMODUR 3600 and DESMODUR N100 whichare aliphatic polyisocyanates based on hexamethylene diisocyanate, eachof which is available from Bayer Corporation (Pittsburgh, Pa.).

Specific examples of wall monomer polyisocyanates include1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI),hydrogenated MDI (H12MDI), xylylene diisocyanate (XDI), tetramethylxyloldiisocyanate (TMXDI), 4,4′-diphenyldimethylmethane diisocyanate, di- andtetraalkyldiphenylmethane diisocyanate, 4,4′-dibenzyl diisocyanate,1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, the isomers oftolylene diisocyanate (TDI), optionally in a mixture,1-methyl-2,4-diisocyanatocyclohexane,1,6-diisocyanato-2,2,4-trimethylhexane,1,6-diisocyanato-2,4,4-trimethylhexane,1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane, chlorinatedand brominated diisocyanates, phosphorus-containing diisocyanates,4,4′-diisocyanatophenylperfluoroethane, tetramethoxybutane1,4-diisocyanate, butane 1,4-diisocyanate, hexane 1,6-diisocyanate(HDI), dicyclohexylmethane diisocyanate, cyclohexane 1,4-diisocyanate,ethylene diisocyanate, phthalic acid bisisocyanatoethyl ester, alsopolyisocyanates with reactive halogen atoms, such as1-chloromethylphenyl 2,4-diisocyanate, 1-bromomethylphenyl2,6-diisocyanate, 3,3-bischloromethyl ether 4,4′-diphenyldiisocyanate.Sulfur-containing polyisocyanates are obtained, for example, by reacting2 mol of hexamethylene diisocyanate with 1 mol of thiodiglycol ordihydroxydihexyl sulfide. Further suitable diisocyanates aretrimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane,1,2-diisocyanatododecane and dimer fatty acid diisocyanate.

Other suitable commercially-available polyisocyanates include LUPRANATEM20 (PMDI, commercially available from BASF containing isocyanate group“NCO” 31.5 wt %), where the average n is 0.7; PAPI 27 (PMDI commerciallyavailable from Dow Chemical having an average molecular weight of 340and containing NCO 31.4 wt %) where the average n is 0.7; MONDUR MR(PMDI containing NCO at 31 wt % or greater, commercially available fromBayer) where the average n is 0.8; MONDUR MR Light (PMDI containing NCO31.8 wt %, commercially available from Bayer) where the average n is0.8; MONDUR 489 (PMDI commercially available from Bayer containing NCO30-31.4 wt %) where the average n is 1.0;poly[(phenylisocyanate)-co-formaldehyde] (Aldrich Chemical, Milwaukee,Wis.), other isocyanate monomers such as DESMODUR N3200(poly(hexamethylene diisocyanate) commercially available from Bayer),and TAKENATE D110-N(xylene diisocyanate adduct polymer commerciallyavailable from Mitsui Chemicals corporation, Rye Brook, N.Y., containingNCO 11.5 wt %), DESMODUR L75 (a polyisocyanate base on toluenediisocyanate commercially available from Bayer), and DESMODUR IL(another polyisocyanate based on toluene diisocyanate commerciallyavailable from Bayer).

In some embodiments, the polyisocyanate used in the preparation of themicrocapsules of this invention is a single polyisocyanate. In otherembodiments the polyisocyanate is a mixture of polyisocyanates. In someembodiments, the mixture of polyisocyanates includes an aliphaticpolyisocyanate and an aromatic polyisocyanate. In particularembodiments, the mixture of polyisocyanates is a biuret of hexamethylenediisocyanate and a trimethylol propane-adduct of xylylene diisocyanate.In certain embodiments, the polyisocyanate is an aliphatic isocyanate ora mixture of aliphatic isocyanate, free of any aromatic isocyanate. Inother words, in these embodiments, no aromatic isocyanate is used toprepare the polyurea/polyureathane polymers as capsule wall materials.

The average molecular weight of certain suitable polyisocyanates variesfrom 250 to 1000 Da and preferable from 275 to 500 Da. In general, therange of the polyisocyanate concentration varies from 0.1% to 10%,preferably from 0.1% to 8%, more preferably from 0.2 to 5%, and evenmore preferably from 1.5% to 3.5%, all based on the weight of thecapsule delivery system.

More examples of suitable polyisocyanates can be found in WO2004/054362; WO 2015/023961; EP 0148149; EP 0017409 B1; U.S. Pat. No.4,417,916, U.S. Pat. No. 4,124,526, U.S. Pat. No. 5,583,090, U.S. Pat.No. 6,566,306, U.S. Pat. No. 6,730,635, WO 1990/08468, WO 1992/13450,U.S. Pat. No. 4,681,806, U.S. Pat. No. 4,285,720 and U.S. Pat. No.6,340,653.

Cross-linkers or cross-linking agents suitable for use withpolyisocyanates each contain multiple (i.e., two or more) functionalgroups (e.g., —NH—, —NH₂ and —OH) that can react with polyisocyanates toform polyureas or polyurethanes. Examples include polyfunctional aminescontaining two or more amine groups (e.g., polyamines), polyfunctionalalcohols containing two or more hydroxyl groups (e.g., polyols), epoxycross-linkers, acrylate cross-linkers, and hybrid cross-linking agentscontaining one or more amine groups and one or more hydroxyl groups.

Amine groups in the cross-linking agents include —NH₂ and —R*NH, R*being substituted and unsubstituted C₁-C₂₀ alkyl, C₁-C₂₀ heteroalkyl,C₁-C₂₀ cycloalkyl, 3- to 8-membered heterocycloalkyl, aryl, andheteroaryl.

Two classes of such polyamines include polyalkylene polyamines havingthe following structures:

in which R is hydrogen or —CH₃; and m, n, x, y, and z each areindependently integers from 0-2000 (e.g., 1, 2, 3, 4 or 5). Examplesinclude ethylene diamine, 1,3-diaminepropane, diethylene triamine,triethylene tetramine, 1,4-diaminobutane, hexaethylene diamine,hexamethylene diamine, pentaethylenehexamine, and the like.

Another class of polyamines are polyalykylene polyamines of the type:

where R equals hydrogen or —CH₃, m is 1-5 and n is 1-5, e.g., diethylenetriamine, triethylene tetraamine and the like. Exemplary amines of thistype also include diethylenetriamine, bis(3-aminopropyl)amine,bis(hexanethylene)triamine.

Another class of amine that can be used in the invention ispolyetheramines. They contain primary amino groups attached to the endof a polyether backbone. The polyether backbone is normally based oneither propylene oxide (PO), ethylene oxide (EO), or mixed PO/EO. Theether amine can be monoamine, diamine, or triamine, based on this corestructure. An example is:

Exemplary polyetheramines include 2,2′-ethylenedioxy)bis (ethylamine)and 4,7,10-trioxa-1,13-tridecanediamine.

Other suitable amines include, but are not limited to,tris(2-aminoethyl)amine, triethylenetetramine,N,N′-bis(3-aminopropyl)-1,3-propanediamine, tetraethylene pentamine,1,2-diaminopropane, N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylene diamine,N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylene diamine, branchedpolyethylenimine, 2,4-diamino-6-hydroxypyrimidine and2,4,6-triaminopyrimidine.

Amphoteric amines, i.e., amines that can react as an acid as well as abase, are another class of amines of use in this invention. Examples ofamphoteric amines include proteins and amino acids such as gelatin,L-lysine, D-lysine, L-arginine, D-arginine, L-lysine monohydrochloride,D-lysine monohydrochloride, L-arginine monohydro chloride, D-argininemonohydro chloride, L-ornithine monohydrochloride, D-ornithinemonohydrochloride or a mixture thereof.

Guanidine amines and guanidine salts are yet another class ofmulti-functional amines of use in this invention. Exemplary guanidineamines and guanidine salts include, but are not limited to,1,3-diaminoguanidine monohydrochloride, 1,1-dimethylbiguanidehydrochloride, guanidine carbonate and guanidine hydrochloride.

Commercially available examples of amines include JEFFAMINE EDR-148having a structure shown above (where n=2), JEFFAMINE EDR-176 (wheren=3) (from Huntsman). Other polyether amines include the JEFFAMINE EDSeries, JEFFAMINE TRIAMINES, polyethylenimines from BASF (Ludwigshafen,Germany) under LUPASOL grades (e.g., LUPASOL FG, LUPASOL G20 waterfree,LUPASOL PR 8515, LUPASOL WF, LUPASOL FC, LUPASOL G20, LUPASOL G35,LUPASOL G100, LUPASOL G500, LUPASOL HF, LUPASOL PS, LUPASOL HEO 1,LUPASOL PN50, LUPASOL PN60, LUPASOL P0100 and LUPASOL SK). Othercommercially available polyethylenimines include EPOMIN P-1000, EPOMINP-1050, EPOMIN RP18W and EPOMIN PP-061 from NIPPON SHOKUBAI (New York,N.Y.). Polyvinylamines such as those sold by BASF under LUPAMINE gradescan also be used. A wide range of polyetheramines may be selected bythose skilled in the art. In certain embodiments, the cross-linkingagent is hexamethylene diamine, polyetheramine or a mixture thereof.

The structures of specific cross-linking agents are shown in Table 1below:

TABLE 1

Diethylenetriamine

Bis(3-aminopropyl)amine

Tris(2-aminoethyl)amine

Bis(hexanethylene)triamine H(NHCH₂CH₂)₅NH₂ Pentaethylenehexamine

Triethylenetetramine

1,3-Diaminoguanidine monohydrochloride

N,N′-Bis(3-aminopropyl)-1,3-propanediamine

1,1-Dimethylbiguanide hydrochloride

Tetraethylenepentamine

Guanidine carbonate

Branched Polyethylenimine

Chitosan

Nisin

Gelatin

Polyfunctional alcohols of use in this invention generally have at leasttwo nucleophilic centers, e.g., ethylene glycol, hexylene glycol,pentaerythritol, glucose, sorbitol, and 2-aminoethanol.

The range of polyfunctional amines, polyfunctional alcohols, or hybridcross-linking agents can vary from 0.1% to 5% (e.g., 0.2% to 3%, 0.2% to2%, 0.5% to 2%, or 0.5% to 1%) by weight of the capsule delivery system.In one embodiment of the invention, the cross-linking agent is added tothe capsule reaction at a temperature of 0-55° C. (e.g., 10-50° C.,15-45° C., 20-40° C., or 22-35° C.).

By adding an excess amount of a cross-linking agent, thepolyurea/polyurethane formation is driven toward completion therebyreducing the amount of residual polyisocyanate. The reactionstoichiometry requires one amine/hydroxyl group per one isocyanategroup. By way of illustration, when combining LUPRANATE M20 (having amolecular weight of 360 and isocyanate functionality of 2.7) andhexamethylenediamine (HMDA; having a molecular weight of 116.21 andamine functionality of 2), the stoichiometry of the system indicatesthat for each gram of HMDA, 2.23 grams of LUPRANATE is needed. Theamount of amine will be in excess if more than one gram of HMDA is usedper 2.23 grams of LUPRANATE M20. Using a cross-linker in excess,residual isocyanate amounts are reduced by at least 30%. After thecapsules are formed, the free cross-link agent (e.g.,hexamethylenediamine, amino-2-methyl-1-propanol, lysine, arginine, andhistidine) can be present in the capsule slurry at a concentration of 20ppm to 2%. The amounts of the residual isocyanate and free cross-linkingagent can be removed by washing the capsule slurry with water orcarbonate/bicarbonate solution (e.g., sodium carbonate, potassiumcarbonate, sodium bicarbonate, and potassium bicarbonate).

Catalysts of use in the preparation of microcapsules include metalcarbonates, metal hydroxide, amino or organometallic compounds such assodium carbonate, cesium carbonate, potassium carbonate, lithiumhydroxide, 1,4-diazabicyclo[2.2.2]octane (i.e., DABCO),N,N-dimethylaminoethanol, N,N-dimethylcyclohexylamine,bis-(2-dimethyl-amino-ethyl) ether, N,N dimethylacetylamine, stannousoctoate and dibutyltin dilaurate.

Polyacrylate/Polyacrylamide/Poly(acrylate-co-acrylamide) Microcapsules.

Preferred polyacrylate precursor are bi- or polyfunctional vinylmonomers including by way of illustration and not limitation, allylmethacrylate/acrylamide, triethylene glycol dimethacrylate/acrylamide,ethylene glycol dimethacrylate/acrylamide, diethylene glycoldimethacrylate/acrylamide, triethylene glycol dimethacrylate/acrylamide,tetraethylene glycol dimethacrylate/acrylamide, propylene glycoldimethacrylate/acrylamide, glycerol dimethacrylate/acrylamide, neopentylglycol dimethacrylate/acrylamide, 1,10-decanedioldimethacrylate/acrylamide, pentaerythritol trimethacrylate/acrylamide,pentaerythritol tetramethacrylate/acrylamide, dipentaerythritolhexamethacrylate/acrylamide, triallyl-formal trimethacrylate/acrylamide,trimethylol propane trimethacrylate/acrylamide, tributanedioldimethacrylate/acrylamide, aliphatic or aromatic urethanediacrylates/acrylamides, difunctional urethane acrylates/acrylamides,ethoxylated aliphatic difunctional urethane methacrylates/acrylamides,aliphatic or aromatic urethane dimethacrylates/acrylamides, epoxyacrylates/acrylamides, epoxymethacrylates/acrylamides, 1,3-butyleneglycol diacrylate/acrylamide, 1,4-butanediol dimethacrylate/acrylamide,1,4-butaneidiol diacrylate/acrylamide, diethylene glycoldiacrylate/acrylamide, 1,6-hexanediol diacrylate/acrylamide,1,6-hexanediol dimethacrylate/acrylamide, neopentyl glycoldiacrylate/acrylamide, polyethylene glycol diacrylate/acrylamide,tetraethylene glycol diacrylate/acrylamide, triethylene glycoldiacrylate/acrylamide, 1,3-butylene glycol dimethacrylate/acrylamide,tripropylene glycol diacrylate/acrylamide, ethoxylated bisphenoldiacrylate/acrylamide, ethoxylated bisphenoldimethylacrylate/acrylamide, dipropylene glycol diacrylate/acrylamide,alkoxylated hexanediol diacrylate/acrylamide, alkoxylated cyclohexanedimethanol diacrylate/acrylamide, propoxylated neopentyl glycoldiacrylate/acrylamide, trimethylol-propane triacrylate/acrylamide,pentaerythritol triacrylate/acrylamide, ethoxylated trimethylolpropanetriacrylate/acrylamide, propoxylated trimethylolpropanetriacrylate/acrylamide, propoxylated glyceryl triacrylate/acrylamide,ditrimethyloipropane tetraacrylate/acrylamide, dipentaerythritolpentaacrylate/acrylamide, ethoxylated pentaerythritoltetraacrylate/acrylamide, PEG 200 dimethacrylate/acrylamide, PEG 400dimethacrylate/acrylamide, PEG 600 dimethacrylate/acrylamide,3-acryloyloxy glycol monoacrylate/acrylamide, triacryl formal, triallylisocyanate, and triallyl isocyanurate.

The monomer is polymerized in the presence of an activation agent (e.g.,an initiator) at an elevated temperature (e.g., 30-90° C.) or under UVlight. Exemplary initiators are 2,2′-azobis(isobutyronitrile) (“AIBN”),dicetyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate,dioctanoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, didecanoylperoxide, tert-butyl peracetate, tert-butyl perlaurate, tert-butylperbenzoate, tert-butyl hydroperoxide, cumene hydroperoxide, cumeneethylperoxide, diisopropylhydroxy dicarboxylate,2,2′-azobis(2,4-dimethylvaleronitrile),1,1′-azobis-(cyclohexane-1-carbonitrile), dimethyl2,2′-azobis(2-methylpropionate),2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide, sodium persulfate,benzoyl peroxide, and combinations thereof.

Emulsifiers used in the formation ofpolyacrylate/polyacrylamide/poly(acrylate-co-acrylamide) capsule wallsare typically anionic emulsifiers including by way of illustration andnot limitation, water-soluble salts of alkyl sulfates, alkyl ethersulfates, alkyl isothionates, alkyl carboxylates, alkyl sulfosuccinates,alkyl succinamates, alkyl sulfate salts such as sodium dodecyl sulfate,alkyl sarcosinates, alkyl derivatives of protein hydrolyzates, acylaspartates, alkyl or alkyl ether or alkylaryl ether phosphate esters,sodium dodecyl sulphate, phospholipids or lecithin, or soaps, sodium,potassium or ammonium stearate, oleate or palmitate, alkylarylsulfonicacid salts such as sodium dodecylbenzenesulfonate, sodiumdialkylsulfosuccinates, dioctyl sulfosuccinate, sodiumdilaurylsulfosuccinate, poly(styrene sulfonate) sodium salt,isobutylene-maleic anhydride copolymer, gum arabic, sodium alginate,carboxymethylcellulose, cellulose sulfate and pectin, poly(styrenesulfonate), isobutylene-maleic anhydride copolymer, gum arabic,carrageenan, sodium alginate, pectic acid, tragacanth gum, almond gumand agar; semi-synthetic polymers such as carboxymethyl cellulose,sulfated cellulose, sulfated methylcellulose, carboxymethyl starch,phosphated starch, lignin sulfonic acid; and synthetic polymers such asmaleic anhydride copolymers (including hydrolyzates thereof),polyacrylic acid, polymethacrylic acid, acrylic acid butyl acrylatecopolymer or crotonic acid homopolymers and copolymers,vinylbenzenesulfonic acid or 2-acryl-amido-2-methylpropanesulfonic acidhomopolymers and copolymers, and partial amide or partial ester of suchpolymers and copolymers, carboxymodified polyvinyl alcohol, sulfonicacid-modified polyvinyl alcohol and phosphoric acid-modified polyvinylalcohol, phosphated or sulfated tristyrylphenol ethoxylates. The amountof anionic emulsifier is anywhere from about 0.1 to about 40 percent byweight of all constituents, more preferably from 0.5 to about 10percent, more preferably 0.5 to 5 percent by weigh.

Polymeric stabilizers are often added to microcapsules containingpolyacrylate, polyacrylamide, or poly(acrylate-co-acrylamide). Suitablestabilizers are cationic cellulose derivatives, quaternized gums,polyethylene imines, cationic polyacrylates, polyacrylamides,polyacrylates, gelatin, quaternized protein hydrolysates, quaternizedamino silicones, hydroxyethyl cellulose, polyvinyl pyrrolidone,polyvinyl alcohol, styrene co-polymer with maleic anhydride or acrylicacid, and combinations thereof.

Silk Fibroin Microcapsules.

Various methods of producing silk fibroin particles are known in theart. In some embodiments, the silk particles can be produced by apolyvinyl alcohol (PVA) phase separation method as described in, e.g.,WO 2011/041395. Other methods for producing silk fibroin particles aredescribed, for example, in US 2010/0028451 and WO 2008/118133 (using oilas a template for making silk microspheres or nanospheres), and in Wenk,et al. (2008) J. Control. Release 132:26-34 (using spraying method toproduce silk microspheres or nanospheres).

In some embodiments, silk particles can be produced using afreeze-drying method as described in WO 2013/155404. Specifically, asilk fibroin foam can be produced by freeze-drying a silk solution. Thefoam then can be reduced to microcapsules. For example, a silk solutioncan be cooled to a temperature at which the liquid carrier transformsinto a plurality of solid crystals or particles and removing at leastsome of the plurality of solid crystals or particles to leave a poroussilk material (e.g., silk foam). After cooling, liquid carrier can beremoved, at least partially, by sublimation, evaporation, and/orlyophilization. See also US 2015/0164117 and US 2015/0202304.

Silica-Based Capsules Produced with Sol-Gel Precursors.

Suitable sol-gel precursors are compounds capable of forming gels suchas compounds containing silicon, boron, aluminum, titanium, zinc,zirconium, and vanadium. Preferred precursors are organosilicon,organoboron, and organoaluminum including metal alkoxides andb-diketonates.

Suitable sol-gel precursors include in particular di-, tri- and/ortetrafunctional silicic acid, boric acid and alumoesters, moreparticularly alkoxysilanes (alkyl orthosilicates), and precursorsthereof.

One example of sol-gel precursors suitable for the purposes of theinvention are alkoxysilanes corresponding to the following generalformula:

(R₁O)(R₂O)M(X)(X′),

wherein X can be hydrogen or —OR₃; X′ can be hydrogen or —OR₄; and R₁,R₂, R₃ and R₄ independently represent an organic group, moreparticularly a linear or branched alkyl group, preferably a C₁-C₁₂alkyl. M can be Si, Ti, or Zr.

A preferred sol/gel precursor is alkoxysilanes corresponding to thefollowing general formula: (R₁O)(R₂O)Si(X)(X), wherein each of X, X′,R₁, and R₂ is defined above.

Particularly preferred compounds are the silicic acid esters such astetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS). Apreferred compound includes Dynasylan® (organofunctional silanescommercially available from Degussa Corporation (Parsippany, N.J.)).Other sol-gel precursors suitable for the purposes of the invention aredescribed, for example, in German Patent Application DE10021165. Thesesol-gel precursors are various hydrolyzable organosilanes such as, forexample, alkylsilanes, alkoxysilanes, alkyl alkoxysilanes andorganoalkoxysilanes. Besides the alkyl and alkoxy groups, other organicgroups (for example, allyl groups, aminoalkyl groups, hydroxyalkylgroups, etc.) may be attached as substituents to the silicon.

Recognizing that metal and semi metal alkoxide monomers (and theirpartially hydrolyzed and condensed polymers) such as tetramethoxy silane(TMOS), tetraethoxy silane (TEOS), etc. are very good solvents fornumerous molecules and active ingredients is highly advantageous sinceit facilitates dissolving the active materials at a high concentrationand thus a high loading in the final capsules.

Additional polymer systems of use in the preparation of microcapsulesinclude, e.g., aminoplast capsules and encapsulated particles asdisclosed in GB 2006709 A; microcapsules having walls composed ofstyrene-maleic anhydride reacted with melamine-formaldehydeprecondensates as disclosed in U.S. Pat. No. 4,396,670; an acrylicacid-acrylamide copolymer, cross-linked with a melamine-formaldehyderesin as disclosed in U.S. Pat. No. 5,089,339; capsules composed ofcationic melamine-formaldehyde condensates as disclosed in U.S. Pat. No.5,401,577; melamine formaldehyde microencapsulation as disclosed in U.S.Pat. No. 3,074,845; amido-aldehyde resin in situ polymerized capsulesdisclosed in EP 0158449 A1; etherified urea-formaldehyde polymer asdisclosed in U.S. Pat. No. 5,204,185; melamine-formaldehydemicrocapsules as described in U.S. Pat. No. 4,525,520; cross-linkedoil-soluble melamine-formaldehyde precondensate as described in U.S.Pat. No. 5,011,634; capsule wall material formed from a complex ofcationic and anionic melamine-formaldehyde precondensates that are thencross-linked as disclosed in U.S. Pat. No. 5,013,473; polymeric shellsmade from addition polymers such as condensation polymers, phenolicaldehydes, urea aldehydes or acrylic polymer as disclosed in U.S. Pat.No. 3,516,941; urea-formaldehyde capsules as disclosed in EP 0443428 A2;melamine-formaldehyde chemistry as disclosed in GB 2062570 A; andcapsules composed of polymer or copolymer of styrene sulfonic acid inacid of salt form, and capsules cross-linked with melamine-formaldehydeas disclosed in U.S. Pat. No. 4,001,140.

Capsule Formation Aids.

Most capsule formation aids are used as dispersants (namely, emulsifiersor surfactants). They facilitate the formation of stable emulsionscontaining nano- or micro-sized oil drops to be encapsulated. Further,capsule formation aids improve the performance of the capsule deliverysystem by stabilizing capsules and/or their deposition to the targetareas or releasing to the environment. Performance is measured by theintensity of the fragrance release during the pre-rub phase andpost-rub. The pre-rub phase is the phase when the capsules have beendeposited on the cloth, e.g., after a fabric softener containingcapsules has been used during the wash cycle. The post-rub phase isafter the capsules have been deposited and the capsules are broken byfriction or other similar mechanisms.

In general, the amount of the capsule formation aid varies from 0.1 to5% (e.g., 0.05 to 0.2%, 0.5 to 4%, 0.2 to 2%, 1 to 2%, or 1% to 3%) byweight of the capsule delivery system.

In some embodiments, the capsule formation aid is a protective colloidor emulsifier including, e.g., maleic-vinyl copolymers such as thecopolymers of vinyl ethers with maleic anhydride or acid, sodiumlignosulfonates, maleic anhydride/styrene copolymers, ethylene/maleicanhydride copolymers, and copolymers of propylene oxide and ethyleneoxide, polyvinylpyrrolidone (PVP), polyvinyl alcohols (PVA), sodium saltof naphthalene sulfonate condensate, carboxymethyl cellulose (CMC),fatty acid esters of polyoxyethylenated sorbitol, sodium dodecylsulfate,and any combination thereof.

Commercially available surfactants include, but are not limited to,sulfonated naphthalene-formaldehyde condensates such as MORWET D425(naphthalene sulfonate, Akzo Nobel, Fort Worth, Tex.); partiallyhydrolyzed polyvinyl alcohols such as MOWIOLs, e.g., MOWIOL 3-83 (AirProducts); ethylene oxide-propylene oxide block copolymers or poloxamerssuch as PLURONIC, SYNPERONIC or PLURACARE materials (BASF); sulfonatedpolystyrenes such as FLEXAN II (Akzo Nobel); ethylene-maleic anhydridepolymers such as ZEMAC (Vertellus Specialties Inc.); and Polyquaterniumseries such as Polyquaternium 11 (“PQ11;” a copolymer of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate; sold byBASF as LUVIQUAT PQ11 AT 1).

In other embodiments, the capsule formation aid is a processing aid suchas hydrocolloids, which improve the colloidal stability of the slurryagainst coagulation, sedimentation and creaming. The term “hydrocolloid”refers to a broad class of water-soluble or water-dispersible polymershaving anionic, cationic, zwitterionic or non-ionic character.Hydrocolloids useful in the present invention include, but are notlimited to, polycarbohydrates, such as starch, modified starch, dextrin,maltodextrin, and cellulose derivatives, and their quaternized forms;natural gums such as alginate esters, carrageenan, xanthanes, agar-agar,pectines, pectic acid, and natural gums such as gum arabic, gumtragacanth and gum karaya, guar gums and quaternized guar gums;gelatine, protein hydrolysates and their quaternized forms; syntheticpolymers and copolymers, such as poly(vinyl pyrrolidone-co-vinylacetate), poly(vinyl alcohol-co-vinyl acetate), poly((met)acrylic acid),poly(maleic acid), poly(alkyl(meth)acrylate-co-(meth)acrylic acid),poly(acrylic acid-co-maleic acid)copolymer, poly(alkyleneoxide),poly(vinylmethylether), poly(vinylether-co-maleic anhydride), and thelike, as well as poly-(ethyleneimine), poly((meth)acrylamide),poly(alkyleneoxide-co-dimethylsiloxane), poly(amino dimethylsiloxane),and the like, and their quaternized forms.

The capsule formation aid may also be used in combination with CMC,polyvinylpyrrolidone, polyvinyl alcohol, alkylnaphthalenesulfonateformaldehyde condensates, and/or a surfactant during processing tofacilitate capsule formation. Examples of surfactants that can be usedin combination with the capsule formation aid include, but are notlimited to, cetyl trimethyl ammonium chloride (CTAC), poloxamers such asPLURONICS (e.g., PLURONIC F127), PLURAFAC (e.g., PLURAFAC F127), orMIRANET-N, saponins such as QNATURALE (National Starch Food Innovation);or a gum Arabic such as Seyal or Senegal. In certain embodiments, theCMC polymer has a molecular weight range between about 90,000 Daltons to1,500,000 Daltons, preferably between about 250,000 Daltons to 750,000Daltons and more preferably between 400,000 Daltons to 750,000 Daltons.The CMC polymer has a degree of substitution between about 0.1 to about3, preferably between about 0.65 to about 1.4, and more preferablybetween about 0.8 to about 1.0. The CMC polymer is present in thecapsule slurry at a level from about 0.1% to about 2% and preferablyfrom about 0.3% to about 0.7%. In other embodiments,polyvinylpyrrolidone used in this invention is a water-soluble polymerand has a molecular weight of 1,000 to 10,000,000. Suitablepolyvinylpyrrolidone are polyvinylpyrrolidone K12, K15, K17, K25, K30,K60, K90, or a mixture thereof. The amount of polyvinylpyrrolidone is2-50%, 5-30%, or 10-25% by weight of the capsule delivery system.Commercially available alkylnaphthalenesulfonate formaldehydecondensates include MORWET D-425, which is a sodium salt of naphthalenesulfonate condensate by Akzo Nobel, Fort Worth, Tex.

Chain Termination Agent.

Polymerization reactions for forming polyurea/polyurethane polymers canbe terminated by adding a chain termination agent, e.g., amonofunctional amine or alcohol. Further, a chain termination agent alsoreacts with isocyanate groups on the surface of the capsules, thusreduced/eliminated isocyanate groups. Examples of a chain terminationagent include C₁-C₂₀ primary and secondary amines, C₁-C₂₀ alcohols,C₁-C₂₀ thiols, and any combination thereof.

Active Material.

The core of the microcapsules of the invention can include one or moreactive materials including, but not limited to, a fragrance,pro-fragrance, flavor, malodor counteractive agent, anti-inflammatoryagent, anesthetic, analgesic, anti-viral agent, anti-infectious agent,anti-acne agent, skin lightening agent, insect repellant, emollient,skin moisturizing agent, vitamin or derivative thereof, nanometer tomicron size inorganic solid, polymeric or elastomeric particle, orcombination thereof. Individual active materials that can beencapsulated include:

i) hydrocarbons, such as, for example, 3-carene, α-pinene, β-pinene,α-terpinene, γ-terpinene, p-cymene, bisabolene, camphene, caryophyllene,cedrene, farnesene, limonene, longifolene, myrcene, ocimene, valencene,(E,Z)-1,3,5-undecatriene, styrene, and diphenylmethane;

ii) aliphatic alcohols, such as, for example, hexanol, octanol,3-octanol, 2,6-dimethyl-heptanol, 2-methyl-2-heptanol,2-methyl-2-octanol, (E)-2-hexenol, (E)- and (Z)-3-hexenol, 1-octen-3-ol,a mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and3,5,6,6-tetramethyl-4-methyleneheptan-2-ol, (E,Z)-2,6-nonadienol,3,7-dimethyl-7-methoxyoctan-2-ol, 9-decenol, 10-undecenol,4-methyl-3-decen-5-ol, aliphatic aldehydes and their acetals such as forexample hexanal, heptanal, octanal, nonanal, decanal, undecanal,dodecanal, tridecanal, 2-methyloctanal, 2-methylnonanal, (E)-2-hexenal,(Z)-4-heptenal, 2,6-dimethyl-5-heptenal, 10-undecenal, (E)-4-decenal,2-dodecenal, 2,6,10-trimethyl-5,9-undecadienal, heptanal-diethylacetal,1,1-dimethoxy-2,2,5-trimethyl-4-hexene, and citronellyl oxyacetaldehyde;

iii) aliphatic ketones and oximes thereof, such as, for example,2-heptanone, 2-octanone, 3-octanone, 2-nonanone, 5-methyl-3-heptanone,5-methyl-3-heptanone oxime, 2,4,4,7-tetra-methyl-6-octen-3-one,aliphatic sulfur-containing compounds, such as for example3-methylthio-hexanol, 3-methylthiohexyl acetate, 3-mercaptohexanol,3-mercaptohexyl acetate, 3-mercapto-hexyl butyrate, 3-acetylthiohexylacetate, 1-menthene-8-thiol, and aliphatic nitriles (e.g.,2-nonenenitrile, 2-tridecenenitrile, 2,12-tridecenenitrile,3,7-dimethyl-2,6-octadienenitrile, and 3,7-dimethyl-6-octenenitrile);

iv) aliphatic carboxylic acids and esters thereof, such as, for example,(E)- and (Z)-3-hexenylformate, ethyl acetoacetate, isoamyl acetate,hexyl acetate, 3,5,5-trimethylhexyl acetate, 3-methyl-2-butenyl acetate,(E)-2-hexenyl acetate, (E)- and (Z)-3-hexenyl acetate, octyl acetate,3-octyl acetate, 1-octen-3-yl acetate, ethyl butyrate, butyl butyrate,isoamyl butyrate, hexylbutyrate, (E)- and (Z)-3-hexenyl isobutyrate,hexyl crotonate, ethylisovalerate, ethyl-2-methyl pentanoate, ethylhexanoate, allyl hexanoate, ethyl heptanoate, allyl heptanoate, ethyloctanoate, ethyl-(E,Z)-2,4-decadienoate, methyl-2-octinate,methyl-2-noninate, allyl-2-isoamyl oxyacetate, andmethyl-3,7-dimethyl-2,6-octadienoate;

v) acyclic terpene alcohols, such as, for example, citronellol,geraniol, nerol, linalool, lavandulol, nerolidol, farnesol,tetrahydrolinalool, tetrahydrogeraniol, 2,6-dimethyl-7-octen-2-ol,2,6-dimethyloctan-2-ol, 2-methyl-6-methylene-7-octen-2-ol,2,6-dimethyl-5,7-octadien-2-ol, 2,6-dimethyl-3,5-octadien-2-ol,3,7-dimethyl-4, 6-octadien-3-ol, 3,7-dimethyl-1,5,7-octatrien-3-ol,2,6-dimethyl-2,5,7-octatrien-1-ol, as well as formates, acetates,propionates, isobutyrates, butyrates, isovalerates, pentanoates,hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates thereof;

vi) acyclic terpene aldehydes and ketones, such as, for example,geranial, neral, citronellal, 7-hydroxy-3,7-dimethyloctanal,7-methoxy-3,7-dimethyloctanal, 2,6,10-trimethyl-9-undecenal, α-sinensal,β-sinensal, geranylacetone, as well as the dimethyl- and diethylacetalsof geranial, neral and 7-hydroxy-3,7-dimethyloctanal;

vii) cyclic terpene alcohols, such as, for example, menthol, isopulegol,alpha-terpineol, terpinen-4-ol, menthan-8-ol, menthan-1-ol,menthan-7-ol, borneol, isoborneol, linalool oxide, nopol, cedrol,ambrinol, vetiverol, guaiol, and the formates, acetates, propionates,isobutyrates, butyrates, isovalerates, pentanoates, hexanoates,crotonates, tiglinates and 3-methyl-2-butenoates of alpha-terpineol,terpinen-4-ol, methan-8-ol, methan-1-ol, methan-7-ol, borneol,isoborneol, linalool oxide, nopol, cedrol, ambrinol, vetiverol, andguaiol;

viii) cyclic terpene aldehydes and ketones, such as, for example,menthone, isomenthone, 8-mercaptomenthan-3-one, carvone, camphor,fenchone, α-ionone, β-ionone, α-n-methylionone, β-n-methylionone,α-isomethylionone, β-isomethylionone, alpha-irone, α-damascone,β-damascone, β-damascenone, δ-damascone, γ-damascone,1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one,1,3,4,6,7,8a-hexahydro-1,1,5,5-tetra-methyl-2H-2,4a-methanonaphthalen-8(5H-)-one,nootkatone, dihydronootkatone; acetylated cedarwood oil (cedryl methylketone);

ix) cyclic alcohols, such as, for example, 4-tert-butylcyclohexanol,3,3,5-trimethylcyclo-hexanol, 3-isocamphylcyclohexanol,2,6,9-trimethyl-Z2,Z5,E9-cyclo-dodecatrien-1-ol,2-iso-butyl-4-methyltetrahydro-2H-pyran-4-ol;

x) cycloaliphatic alcohols, such as, for example, alpha,3,3-trimethylcyclo-hexylmethanol,2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol,2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol,2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol,3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-pentan-2-ol,3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol,3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol,1-(2,2,6-trimethylcyclohexyl)pentan-3-ol,1-(2,2,6-trimethylcyclohexyl)hexan-3-ol;

xi) cyclic and cycloaliphatic ethers, such as, for example, cineole,cedryl methyl ether, cyclododecyl methyl ether;

xii) (ethoxymethoxy)cyclododecane; alpha-cedrene epoxide,3a,6,6,9a-tetramethyl-dodecahydronaphtho[2,1-b]furan,3a-ethyl-6,6,9a-trimethyldodecahydro-naphtho[2,1-b]furan,1,5,9-trimethyl-13-oxabicyclo[10.1.0]-trideca-4,8-diene, rose oxide,2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxan-;

xiii) cyclic ketones, such as, for example, 4-tert.-butylcyclohexanone,2,2,5-trimethyl-5-pentylcyclopentanone, 2-heptylcyclopentanone,2-pentylcyclopentanone, 2-hydroxy-3-methyl-2-cyclopenten-1-one,3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one,3-methyl-2-pentyl-2-cyclopenten-1-one, 3-methyl-4-cyclopentadecenone,3-methyl-1-cyclopentadecenone, 3-methylcyclopentadecanone,4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone,4-tert.-pentylcyclohexanone, 5-cyclohexadecen-1-one,6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone,5-cyclohexadecen-1-one, 8-cyclohexadecen-1-one, 9-cycloheptadecen-1-one,cyclopentadecanone, cycloaliphatic aldehydes, such as, for example,2,4-dimethyl-3-cyclohexene carbaldehyde,2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal,4-(4-hydroxy-4-methylpentyl)-3-cyclohexene carbaldehyde,4-(4-methyl-3-penten-1-yl)-3-cyclohexene carbaldehyde;

xiv) cycloaliphatic ketones, such as, for example,1-(3,3-dimethylcyclohexyl)-4-penten-1-one,1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphtalenyl methyl-ketone,methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone,tert-butyl-(2,4-dimethyl-3-cyclohexen-1-yl)ketone;

xv) esters of cyclic alcohols, such as, for example,2-tert-butylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate,2-tert-pentylcyclohexyl acetate, 4-tert-pentylcyclohexyl acetate,decahydro-2-naphthyl acetate, 3-pentyltetrahydro-2H-pyran-4-yl acetate,decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate,4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate,4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate,4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl-isobutyrate,4,7-methanooctahydro-5 or 6-indenyl acetate;

xvi) esters of cycloaliphatic carboxylic acids, such as, for example,allyl 3-cyclohexyl-propionate, allyl cyclohexyl oxyacetate, methyldihydrojasmonate, methyl jasmonate, methyl2-hexyl-3-oxocyclopentanecarboxylate, ethyl2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate, ethyl2,3,6,6-tetramethyl-2-cyclohexenecarboxylate, ethyl 2-methyl-1,3-dioxolane-2-acetate;

xvii) aromatic and aliphatic alcohols, such as, for example, benzylalcohol, 1-phenylethyl alcohol, 2-phenylethyl alcohol, 3-phenylpropanol,2-phenylpropanol, 2-phenoxyethanol, 2,2-dimethyl-3-phenylpropanol,2,2-dimethyl-3-(3-methylphenyl)-propanol, 1,1-dimethyl-2-phenylethylalcohol, 1,1-dimethyl-3-phenylpropanol,1-ethyl-1-methyl-3-phenylpropanol, 2-methyl-5-phenylpentanol,3-methyl-5-phenylpentanol, 3-phenyl-2-propen-1-ol, 4-methoxybenzylalcohol, 1-(4-isopropylphenyl)ethanol;

xviii) esters of aliphatic alcohols and aliphatic carboxylic acids, suchas, for example, benzyl acetate, benzyl propionate, benzyl isobutyrate,benzyl isovalerate, 2-phenylethyl acetate, 2-phenylethyl propionate,2-phenylethyl isobutyrate, 2-phenylethyl isovalerate, 1-phenylethylacetate, α-trichloromethylbenzyl acetate, α,α-dimethylphenylethylacetate, alpha, alpha-dimethylphenylethyl butyrate, cinnamyl acetate,2-phenoxyethyl isobutyrate, 4-methoxybenzyl acetate, araliphatic ethers,such as for example 2-phenylethyl methyl ether, 2-phenylethyl isoamylether, 2-phenylethyl-1-ethoxyethyl ether, phenylacetaldehyde dimethylacetal, phenylacetaldehyde diethyl acetal, hydratropaaldehyde dimethylacetal, phenylacetaldehyde glycerol acetal,2,4,6-trimethyl-4-phenyl-1,3-dioxane,4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxin,4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxin;

xix) aromatic and aliphatic aldehydes, such as, for example,benzaldehyde; phenylacetaldehyde, 3-phenylpropanal, hydratropaldehyde,4-methylbenzaldehyde, 4-methylphenyl-acetaldehyde,3-(4-ethylphenyl)-2,2-dimethylpropanal,2-methyl-3-(4-isopropylphenyl)prop anal,2-methyl-3-(4-tert-butylphenyl)propanal,3-(4-tert-butyl-phenyl)propanal, cinnamaldehyde,alpha-butylcinnamaldehyde, alpha-amyl-cinnamaldehyde,alpha-hexylcinnamaldehyde, 3-methyl-5-phenylpentanal,4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde,4-hydroxy-3-ethoxy-benzaldehyde, 3,4-methylene-dioxybenzaldehyde,3,4-dimethoxybenzaldehyde, 2-methyl-3-(4-methoxyphenyl)propanal,2-methyl-3-(4-methylendioxyphenyl)propanal;

xx) aromatic and aliphatic ketones, such as, for example, acetophenone,4-methylaceto-phenone, 4-methoxyacetophenone,4-tert-butyl-2,6-dimethylacetophenone, 4-phenyl-2-butanone,4-(4-hydroxyphenyl)-2-butanone, 1-(2-naphthalenyl)ethanone,benzophenone, 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone,6-ten-butyl-1,1-dimethyl-4-indanyl methyl ketone,1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone,5′,6′,7′,8′-tetrahydro-3′,5′,5′,6′,8′,8′-hexamethyl-2-aceto-naphthone;

xxi) aromatic and araliphatic carboxylic acids and esters thereof, suchas, for example, benzoic acid, phenylacetic acid, methyl benzoate, ethylbenzoate, hexyl benzoate, benzyl benzoate, methyl phenylacetate, ethylphenylacetate, geranyl phenylacetate, phenylethyl phenylacetate, methylcinnamate, ethyl cinnamate, benzyl cinnamate, phenylethyl cinnamate,cinnamyl cinnamate, allyl phenoxyacetate, methyl salicylate, isoamylsalicylate, hexyl salicylate, cyclohexyl salicylate, cis-3-hexenylsalicylate, benzyl salicylate, phenylethyl salicylate, methyl2,4-dihydroxy-3,6-dimethylbenzoate, ethyl 3-phenylglycidate, ethyl3-methyl-3-phenylglycidate;

xxii) nitrogen-containing aromatic compounds, such as, for example,2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene,3,5-dinitro-2,6-dimethyl-4-tert-butylaceto-phenone, cinnamonitrile,-phenyl-3-methyl-2-pentenonitrile, 5-phenyl-3-methylpentano-nitrile,methyl anthranilate, methy-N-methylanthranilate, Schiff's bases ofmethyl anthranilate with 7-hydroxy-3,7-dimethyl-octanal,2-methyl-3-(4-tert-butylphenyl)-propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde, 6-isopropylquinoline, 6-isobutylquinoline,6-sec-butylquinoline, indole, skatole, 2-methoxy-3-isopropylpyrazine,2-isobutyl-3-methoxypyrazine;

xxiii) phenols, phenyl ethers and phenyl esters, such as, for example,estragole, anethole, eugenol, eugenyl methyl ether, isoeugenol,isoeugenol methyl ether, thymol, carvacrol, diphenyl ether,beta-naphthyl methyl ether, beta-naphthyl ethyl ether, beta-naphthylisobutyl ether, 1,4-dimethoxybenzene, eugenyl acetate,2-methoxy-4-methylphenol, 2-ethoxy-5-(1-propenyl)phenol, p-cresylphenylacetate;

xxiv) heterocyclic compounds, such as, for example,2,5-dimethyl-4-hydroxy-2H-furan-3-one,2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one,3-hydroxy-2-methyl-4H-pyran-4-one, 2-ethyl-3-hydroxy-4H-pyran-4-one;

xxv) lactones, such as, for example, 1,4-octanolide,3-methyl-1,4-octanolide, 1,4-nonanolide, 1,4-decanolide,8-decen-1,4-olide, 1,4-undecanolide, 1,4-dodecanolide, 1,5-decanolide,1,5-dodecanolide, 1,15-pentadecanolide, cis- andtrans-11-pentadecen-1,15-olide, cis- and trans-12-pentadecen-1,15-olide,1,16-hexadecanolide, 9-hexadecen-1,16-olide, 10-oxa-1,16-hexadecanolide,11-oxa-1,16-hexadecanolide, 12-oxa-1,16-hexadecanolide,ethylene-1,12-dodecanedioate, ethylene-1,13-tridecanedioate, coumarin,2,3-dihydrocoumarin, and octahydrocoumarin;

xxvi) essential oils, concretes, absolutes, resins, resinoids, balsams,tinctures such as for example ambergris tincture, amyris oil, angelicaseed oil, angelica root oil, aniseed oil, valerian oil, basil oil, treemoss absolute, bay oil, armoise oil, benzoe resinoid, bergamot oil,beeswax absolute, birch tar oil, bitter almond oil, savory oil, buchuleaf oil, cabreuva oil, cade oil, calamus oil, camphor oil, cananga oil,cardamom oil, cascarilla oil, cassia oil, cassie absolute, castoreumabsolute, cedar leaf oil, cedar wood oil, cistus oil, citronella oil,lemon oil, copaiba balsam, copaiba balsam oil, coriander oil, costusroot oil, cumin oil, cypress oil, davana oil, dill weed oil, dill seedoil, eau de brouts absolute, oakmoss absolute, elemi oil, estragon oil,eucalyptus citriodora oil, eucalyptus oil (cineole type), fennel oil,fir needle oil, galbanum oil, galbanum resin, geranium oil, grapefruitoil, guaiacwood oil, gurjun balsam, gurjun balsam oil, helichrysumabsolute, helichrysum oil, ginger oil, iris root absolute, iris rootoil, jasmine absolute, calamus oil, blue camomile oil, Roman camomileoil, carrot seed oil, cascarilla oil, pine needle oil, spearmint oil,caraway oil, labdanum oil, labdanum absolute, labdanum resin, lavandinabsolute, lavandin oil, lavender absolute, lavender oil, lemon-grassoil, lovage oil, lime oil distilled, lime oil expressed, linaloe oil,Litsea cubeba oil, laurel leaf oil, mace oil, marjoram oil, mandarinoil, massoi (bark) oil, mimosa absolute, ambrette seed oil, musktincture, clary sage oil, nutmeg oil, myrrh absolute, myrrh oil, myrtleoil, clove leaf oil, clove bud oil, neroli oil, olibanum absolute,olibanum oil, opopanax oil, orange flower absolute, orange oil, origanumoil, palmarosa oil, patchouli oil, perilla oil, Peru balsam oil, parsleyleaf oil, parsley seed oil, petitgrain oil, peppermint oil, pepper oil,pimento oil, pine oil, pennyroyal oil, rose absolute, rosewood oil, roseoil, rosemary oil, Dalmatian sage oil, Spanish sage oil, sandal-woodoil, celery seed oil: spike-lavender oil, star anise oil, storax oil,tagetes oil, fir needle oil, tea tree oil, turpentine oil, thyme oil,Tolu balsam, tonka bean absolute, tuberose absolute, vanilla extract,violet leaf absolute, verbena oil, vetiver oil, juniperberry oil, winelees oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil,civet absolute, cinnamon leaf oil, cinnamon bark oil, and fractionsthereof or ingredients isolated therefrom;

xxvii) flavors including, but are not limited to, acetaldehyde, dimethylsulfide, ethyl acetate, ethyl propionate, methyl butyrate, and ethylbutyrate. Flavors containing volatile aldehydes or esters include, e.g.,cinnamyl acetate, cinnamaldehyde, citral, diethylacetal, dihydrocarvylacetate, eugenyl formate, and p-methylanisole. Further examples ofvolatile compounds that may be present in the instant flavor oilsinclude acetaldehyde (apple); benzaldehyde (cherry, almond); cinnamicaldehyde (cinnamon); citral, i.e., alpha citral (lemon, lime); neral,i.e., beta citral (lemon, lime); decanal (orange, lemon); ethyl vanillin(vanilla, cream); heliotropine, i.e., piperonal (vanilla, cream);vanillin (vanilla, cream); alpha-amyl cinnamaldehyde (spicy fruityflavors); butyraldehyde (butter, cheese); valeraldehyde (butter,cheese); citronellal (modifies, many types); decanal (citrus fruits);aldehyde C-8 (citrus fruits); aldehyde C-9 (citrus fruits); aldehydeC-12 (citrus fruits); 2-ethyl butyraldehyde (berry fruits); hexenal,i.e., trans-2 (berry fruits); tolyl aldehyde (cherry, almond);veratraldehyde (vanilla); 2,6-dimethyl-5-heptenal, i.e., melonal(melon); 2-6-dimethyloctanal (green fruit); and 2-dodecenal (citrus,mandarin); cherry; or grape and mixtures thereof. The composition mayalso contain taste modulators and artificial sweeteners. As used herein,flavor is understood to include spice oleoresins derived from allspice,basil, capsicum, cinnamon, cloves, cumin, dill, garlic, marjoram,nutmeg, paprika, black pepper, rosemary, and turmeric, essential oils,anise oil, caraway oil, clove oil, eucalyptus oil, fennel oil, garlicoil, ginger oil, peppermint oil, onion oil, pepper oil, rosemary oil,spearmint oil, citrus oil, orange oil, lemon oil, bitter orange oil,tangerine oil, alliaceous flavors, garlic, leek, chive, and onion,botanical extracts, arnica flower extract, chamomile flower extract,hops extract, marigold extract, botanical flavor extracts, blackberry,chicory root, cocoa, coffee, kola, licorice root, rose hips,sarsaparilla root, sassafras bark, tamarind and vanilla extracts,protein hydrolysates, hydrolyzed vegetable proteins, meat proteinhydrolyzes, milk protein hydrolyzates and compounded flavors bothnatural and artificial including those disclosed in S. Heath, SourceBook of Flavors, Avi Publishing Co., Westport Conn., 1981, pages149-277. Specific preferred flavor adjuvants include, but are notlimited to, the following: anise oil; ethyl-2-methyl butyrate; vanillin;cis-3-heptenol; cis-3-hexenol; trans-2-heptenal; butyl valerate;2,3-diethyl pyrazine; methylcyclo-pentenolone; benzaldehyde; valerianoil; 3,4-dimeth-oxyphenol; amyl acetate; amyl cinnamate, γ-butyryllactone; furfural; trimethyl pyrazine; phenyl acetic acid;isovaleraldehyde; ethyl maltol; ethyl vanillin; ethyl valerate; ethylbutyrate; cocoa extract; coffee extract; peppermint oil; spearmint oil;clove oil; anethol; cardamom oil; wintergreen oil; cinnamic aldehyde;ethyl-2-methyl valerate; γ-hexenyl lactone; 2,4-decadienal;2,4-heptadienal; methyl thiazole alcohol (4-methyl-5-b-hydroxyethylthiazole); 2-methyl butanethiol; 4-mercapto-2-butanone;3-mercapto-2-pentanone; 1-mercapto-2-propane; benzaldehyde; furfural;furfuryl alcohol; 2-mercapto propionic acid; alkyl pyrazine; methylpyrazine; 2-ethyl-3-methyl pyrazine; tetramethyl pyrazine; polysulfides;dipropyl disulfide; methyl benzyl disulfide; alkyl thiophene;2,3-dimethyl thiophene; 5-methyl furfural; acetyl furan; 2,4-decadienal;guiacol; phenyl acetaldehyde; decalactone; D-limonene; acetoin; amylacetate; maltol; ethyl butyrate; levulinic acid; piperonal; ethylacetate; n-octanal; n-pentanal; n-hexanal; diacetyl; monosodiumglutamate; monopotassium glutamate; sulfur-containing amino acids, e.g.,cysteine; hydrolyzed vegetable protein; 2-methylfuran-3-thiol;2-methyldihydrofuran-3-thiol; 2,5-dimethylfuran-3-thiol; hydrolyzed fishprotein; tetramethyl pyrazine; propylpropenyl disulfide; propylpropenyltrisulfide; diallyl disulfide; diallyl trisulfide; dipropenyl disulfide;dipropenyl trisulfide; 4-methyl-2-[(methylthio)-ethyl]-1,3-dithiolane;4,5-dimethyl-2-(methylthiomethyl)-1,3-dithiolane;4-methyl-2-(methylthiomethyl)-1,3-dithiolane, and the flavor ingredientsdescribed in U.S. Pat. No. 6,110,520 and U.S. Pat. No. 6,333,180;

xxviii) taste masking agents, substances for masking one or moreunpleasant taste sensations, in particular a bitter, astringent and/ormetallic taste sensation or aftertaste. Examples include lactisol[2O-(4-methoxyphenyl) lactic acid] (see U.S. Pat. No. 5,045,336),2,4-dihydroxybenzoic acid potassium salt (see U.S. Pat. No. 5,643,941),ginger extracts (see GB 2,380,936), neohesperidine dihydrochalcone (seeManufacturing Chemist (2000) 71:16-17), specific flavones(2-phenylchrom-2-en-4-ones) (see U.S. Pat. No. 5,580,545), specificnucleotides, for example cytidine-5′-monophosphates (CMP) (see US2002/0177576), specific sodium salts, such as sodium chloride, sodiumcitrate, sodium acetate and sodium lactate (see Breslin & Beauchamp(1997) Nature 387:563), a lipoprotein of (3-lactoglobulin andphosphatidic acid (see EP 635218), neodiosmine[5,7-dihydroxy-2-(4-methoxy-3-hydroxyphenyl)-7-O-neohesperidosyl-chrom-2-en-4-one](see U.S. Pat. No. 4,154,862), preferably hydroxyflavanones according toEP 1258200, in turn preferred in this respect2-(4-hydroxyphenyl)-5,7-dihydroxychroman-4-one (naringenin),2-(3,4-dihydroxyphenyl)-5,7-dihydroxychroman-4-one (eriodictyol),2-(3,4-dihydroxyphenyl)-5-hydroxy-7-methoxychroman-4-one(eriodictyol-7-methylether),2-(3,4-dihydroxyphenyl)-7-hydroxy-5-methoxychroman-4-one(eriodictyol-5-methylether) and2-(4-hydroxy-3-methoxyphenyl)-5,7-dihydroxychroman-4-one(homoeriodictyol), the (2S)— or (2R)-enantiomers thereof or mixturesthereof as well as the mono- or polyvalent phenolate salts thereof withNa⁺, K⁺, NH4⁺, Ca²⁺, Mg²⁺ or Al³⁺ as counter cations or γ-aminobutyricacid (4-aminobutyric acid, as the neutral form (“inner salt”) or in thecarboxylate or ammonium form) according to WO 2005/09684;

xxix) taste sensates including hot tasting, salivation-inducingsubstances, substances causing a warmth or tingling feeling, and coolingactive ingredients. Examples of hot tasting and/or salivation-inducingsubstances and/or substances which cause a feeling of warmth and/or atingling feeling on the skin or on the mucous membranes and which can bea constituent of the products according to the invention are: capsaicin,dihydrocapsaicin, gingerol, paradol, shogaol, piperine, carboxylicacid-N-vanillylamides, in particular nonanoic acid-N-vanillylamide,pellitorin or spilanthol, 2-nonanoic acid amides, in particular2-nonanoic acid-N-isobutylamide, 2-nonanoicacid-N-4-hydroxy-3-methoxyphenylamide, alkyl ethers of4-hydroxy-3-methoxybenzyl alcohol, in particular4-hydroxy-3-methoxybenzyl-n-butylether, alkyl ethers of4-acyloxy-3-methoxybenzyl alcohol, in particular4-acetyloxy-3-methoxybenzyl-n-butylether and4-acetyloxy-3-methoxybenzyl-n-hexylether, alkyl ethers of3-hydroxy-4-methoxybenzyl alcohol, alkyl ethers of 3,4-dimethoxybenzylalcohol, alkyl ethers of 3-ethoxy-4-hydroxybenzyl alcohol, alkyl ethersof 3,4-methylene dioxybenzyl alcohol, (4-hydroxy-3-methoxyphenyl)aceticacid amides, in particular (4-hydroxy-3-methoxyphenyl)aceticacid-N-n-octylamide, vanillomandelic acid alkylamides, ferulicacid-phenethylamides, nicotinaldehyde, methylnicotinate,propylnicotinate, 2-butoxyethylnicotinate, benzylnicotinate,1-acetoxychavicol, polygodial and isodrimeninol, further preferred cis-and/or trans-pellitorin according to WO 2004/000787 or WO 2004/043906,alkenecarboxylic acid-N-alkylamides according to WO 2005/044778,mandelic acid alkylamides according to WO 03/106404 or alkyloxyalkanoicacid amides according to WO 2006/003210. Examples of preferred hottasting natural extracts and/or natural extracts which cause a feelingof warmth and/or a tingling feeling on the skin or on the mucousmembranes and which can be a constituent of the products according tothe invention are: extracts of paprika, extracts of pepper (for examplecapsicum extract), extracts of chili pepper, extracts of ginger roots,extracts of Aframomum melgueta, extracts of Spilanthes acmella, extractsof Kaempferia galangal or extracts of Alpinia galanga. Suitable coolingactive ingredients include the following: L-menthol, D-menthol, racemicmenthol, menthone glycerol acetal (tradename: FRESCOLAT MGA), menthyllactate (tradename: FRESCOLAT ML), menthyl lactate preferably beingL-menthyl lactate, in particular L-menthyl-L-lactate), substitutedmenthyl-3-carboxamides (for example menthyl-3-carboxylicacid-N-ethylamide), 2-isopropyl-N-2,3-trimethyl-butanamide, substitutedcyclohexane carboxamides, 3-menthoxypropane-1,2-diol, 2-hydroxyethylmenthyl carbonate, 2-hydroxypropyl menthyl carbonate, N-acetylglycinementhyl ester, isopulegol, hydroxycarboxylic acid menthyl esters (forexample menthyl-3-hydroxybutyrate), monomenthyl succinate,2-mercaptocyclodecanone, menthyl-2-pyrrolidin-5-onecarboxylate,2,3-dihydroxy-p-menthane, 3,3,5-trimethylcyclohexanone glycerol ketal,3-menthyl-3,6-di- and -trioxaalkanoates, 3-menthyl methoxyacetate andicilin. Cooling active ingredients which are particularly preferred areas follows: L-menthol, racemic menthol, menthone glycerol acetal(tradename: FRESCOLAT MGA), menthyl lactate (preferably L-menthyllactate, in particular L-menthyl-L-lactate (tradename: FRESCOLAT ML),3-menthoxypropane-1,2-diol, 2-hydroxyethyl menthyl carbonate,2-hydroxypropyl menthyl carbonate.

xxx) malodor counteracting agents including an α,β-unsaturated carbonylcompounds including but not limited to those disclosed in U.S. Pat. No.6,610,648 and EP 2,524,704, amyl cinnamaldehyde, benzophenone, benzylbenzoate, benzyl isoeugenol, benzyl phenyl acetate, benzyl salicylate,butyl cinnamate, cinnamyl butyrate, cinnamyl isovalerate, cinnamylpropionate, decyl acetate, ethyl myristate, isobutyl cinnamate, isoamylsalicylate, phenethyl benzoate, phenethyl phenyl acetate, triethylcitrate, tripropylene glycol n-butyl ether, isomers ofbicyclo[2.2.1]hept-5-ene-2-carboxylic acid, ethyl ester, nano silver,zinc undecenylate, β-naphthyl methyl ether, β-naphthyl ketone, benzylacetone. They may include mixture of hexahydro-4,7-methanoinden-5-ylpropionate and hexahydro-4,7-methanoinden-6-yl propionate;4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-methyl-3-buten-2-one;3,7-dimethyl-2, 6-nonadien-1-nitrile;dodeca-hydro-3a,6,6,9a-tetramethylnaphtho(2,1-b)furan; ethylene glycolcyclic ester of n-dodecanedioic acid; 1-cyclohexadecen-6-one;1-cycloheptadecen-10-one; and corn mint oil. They may also include1-cyclohexylethan-1-yl butyrate; 1-cyclohexylethan-1-yl acetate;1-cyclohexylethan-1-ol; 1-(4′-methylethyl)cyclohexylethan-1-ylpropionate; and 2′-hydroxy-1′-ethyl(2-phenoxy)acetate each of whichcompound is marketed under the trademark VEILEX by International Flavors& Fragrances Inc. More suitable malodor counteracting agents arepolymers containing an α-keto, benzaldehyde, or α,β-unsaturated carbonylmoiety, such as those described in US Application Publications2012/0294821, 2013/0101544 and 2013/0101545;

xxxi) vitamins including any vitamin, a derivative thereof and a saltthereof. Examples are as follows: vitamin A and its analogs andderivatives (e.g., retinol, retinal, retinyl palmitate, retinoic acid,tretinoin, and iso-tretinoin, known collectively as retinoids), vitaminE (tocopherol and its derivatives), vitamin C (L-ascorbic acid and itsesters and other derivatives), vitamin B3 (niacinamide and itsderivatives), alpha hydroxy acids (such as glycolic acid, lactic acid,tartaric acid, malic acid, citric acid, etc.) and beta hydroxy acids(such as salicylic acid and the like);

xxxii) antibacterials including bisguanidines (e.g., chlorhexidinedigluconate), diphenyl compounds, benzyl alcohols, trihalocarbanilides,quaternary ammonium compounds, ethoxylated phenols, and phenoliccompounds, such as halo-substituted phenolic compounds, like PCMX (i.e.,p-chloro-m-xylenol), triclosan (i.e.,2,4,4′-trichloro-2′-hydroxy-diphenylether), thymol, and triclocarban;

xxxiii) sunscreen actives including oxybenzone, octylmethoxy cinnamate,butylmethoxy dibenzoyln ethane, p-aminobenzoic acid and octyldimethyl-p-aminobenzoic acid;

xxxiv) antioxidants such as beta-carotene, vitamin C (Ascorbic Acid) oran ester thereof, vitamin A or an ester thereof, vitamin E or an esterthereof, lutein or an ester thereof, lignan, lycopene, selenium,flavonoids, vitamin-like antioxidants such as coenzyme Q10 (CoQ10) andglutathione, and antioxidant enzymes such as superoxide dismutase (SOD),catalase, and glutathione peroxidase;

xxxv) anti-inflammatory agents including, e.g., methyl salicylate,aspirin, ibuprofen, and naproxen. Additional anti-inflammatories usefulin topical applications include corticosteroids, such as, but notlimited to, flurandrenolide, clobetasol propionate, halobetasolpropionate, fluticasone propionate, betamethasone dipropionate,betamethasone benzoate, betamethasone valerate, desoximethasone,dexamethasone, diflorasone diacetate, mometasone furoate, amcinodine,halcinonide, fluocinonide, fluocinolone acetonide, desonide,triamcinolone acetonide, hydrocortisone, hydrocortisone acetate,fluoromethalone, methylprednisolone, and predinicarbate;

xxxvi) anesthetics that can be delivered locally including benzocaine,butamben, butamben picrate, cocaine, procaine, tetracaine, lidocaine andpramoxine hydrochloride;

xxxvii) analgesics such as ibuprofen, diclofenac, capsaicin, andlidocaine;

xxxviii) antifungal agents including, but not limited to, micanazole,clotrimazole, butoconazole, fenticonasole, tioconazole, terconazole,sulconazole, fluconazole, haloprogin, ketonazole, ketoconazole,oxinazole, econazole, itraconazole, torbinafine, nystatin andgriseofulvin;

xxxix) antibiotics such as erythromycin, clindamycin, synthomycin,tetracycline, metronidazole and the like;

xl) anti-viral agents including famcyclovir, valacyclovir and acyclovir;

xli) anti-parasitic agents such as scabicedes, such as permethrin,crotamiton, lindane and ivermectin;

xlii) anti-infectious and anti-acne agents including benzoyl peroxide,sulfur, resorcinol and salicylic acid;

xliii) dermatological active ingredients useful in topical applicationsincluding, e.g., jojoba oil and aromatic oils such as methyl salicylate,wintergreen, peppermint oil, bay oil, eucalyptus oil and citrus oils, aswell as ammonium phenolsulfonate, bismuth subgallate, zincphenolsulfonate and zinc salicylate;

xliv) enzymes and co-enzymes useful for topical application includingcoenzyme Q10, papain enzyme, lipases, proteases, superoxide dismutase,fibrinolysin, desoxyribonuclease, trypsin, collagenase and sutilains;

xlv) skin whitening or lightening agents such as hydroquinone andmonobenzone;

xlvi) anti-histamines including chlorpheniramine, brompheniramine,dexchlorpheniramine, tripolidine, clemastine, diphenhydramine,prometazine, piperazines, piperidines, astemizole, loratadine andterfonadine;

xlvii) chemotherapeutic agents such as 5-fluorouracil, masoprocol,mechlorethamine, cyclophosphamide, vincristine, chlorambucil,streptozocin, methotrexate, bleomycin, dactinomycin, daunorubicin,coxorubicin and tamoxifen; and

xlviii) insect repellents including pediculicides for treatment of lice,such as pyrethrins, permethrin, malathion, lindane and the like.

In addition to the active materials listed above, the microcapsules ofthis invention can also contain, for example, the following dyes,colorants or pigments: lactoflavin (riboflavin), beta-carotene,riboflavin-5′-phosphate, alpha-carotene, gamma-carotene, cantaxanthin,erythrosine, curcumin, quinoline yellow, yellow orange S, tartrazine,bixin, norbixin (annatto, orlean), capsanthin, capsorubin, lycopene,beta-apo-8′-carotenal, beta-apo-8′-carotenic acid ethyl ester,xantophylls (flavoxanthin, lutein, cryptoxanthin, rubixanthin,violaxanthin, rodoxanthin), fast carmine (carminic acid, cochineal),azorubin, cochineal red A (Ponceau 4 R), beetroot red, betanin,anthocyanins, amaranth, patent blue V, indigotine I (indigo-carmine),chlorophylls, copper compounds of chlorophylls, acid brilliant green BS(lissamine green), brilliant black BN, vegetable carbon, titaniumdioxide, iron oxides and hydroxides, calcium carbonate, aluminum,silver, gold, pigment rubine BK (lithol rubine BK), methyl violet B,victoria blue R, victoria blue B, acilan brilliant blue FFR (brilliantwool blue FFR), naphthol green B, acilan fast green 10 G (alkali fastgreen 10 G), ceres yellow GRN, sudan blue II, ultramarine,phthalocyanine blue, phthalocayanine green, fast acid violet R. Furthernaturally obtained extracts (for example paprika extract, black carrotextract, red cabbage extract) can be used for coloring purposes. Goodsresults are also achieved with the colors named in the following, theso-called aluminum lakes: FD & C Yellow 5 Lake, FD & C Blue 2 Lake, FD &C Blue 1 Lake, Tartrazine Lake, Quinoline Yellow Lake, FD & C Yellow 6Lake, FD & C Red 40 Lake, Sunset Yellow Lake, Carmoisine Lake, AmaranthLake, Ponceau 4R Lake, Erythrosyne Lake, Red 2G Lake, Allura Red Lake,Patent Blue V Lake, Indigo Carmine Lake, Brilliant Blue Lake, Brown HTLake, Black PN Lake, Green S Lake and mixtures thereof.

When the active material is a fragrance, it is preferred that fragranceingredients within a fragrance having a ClogP of 0.5 to 15 are employed.For instance, the ingredients having a ClogP value between 0.5 and 8(e.g., between 1 to 12, between 1.5 to 8, between 2 and 7, between 1 and6, between 2 and 6, between 2 and 5, or between 3 and 7) are 25% orgreater (e.g., 50% or greater and 90% or greater) by the weight of thefragrance.

In some embodiments, it is preferred that a fragrance having aweight-averaged ClogP of 2.5 and greater (e.g., 3 or greater, 2.5 to 7,or 2.5 to 5) is employed. The weight-averaged ClogP is calculated asfollows:

ClogP={Sum[(Wi)(ClogP)i]}/{Sum Wi},

in which Wi is the weight fraction of each fragrance ingredient and(ClogP)i is the ClogP of that fragrance ingredient.

As an illustration, it is preferred that greater than 60 weight percent,preferably greater than 80 and more preferably greater than 90 weightpercent of the fragrance chemicals have ClogP values of greater than 2,preferably greater than 3.3, more preferably greater than 4, and evenmore preferably greater than 4.5.

In other embodiments, the ingredients having a ClogP value between 2 and7 (e.g., between 2 and 6, or between 2 and 5) are 25% or greater (e.g.,50% or greater or 90% or greater) by the weight of the fragrance. Instill other embodiments, it is preferred that greater than 60%,preferably greater than 80% and more preferably greater than 90% of thefragrance chemicals have Clog P values of greater than 3.3, preferablygreater than 4 and most preferably greater than 4.5.

Those with skill in the art will appreciate that many fragrances can becreated employing various solvents and fragrance chemicals. The use of arelatively low to intermediate ClogP fragrance ingredients will resultin fragrances that are suitable for encapsulation. These fragrances aregenerally water-insoluble, to be delivered through the capsule systemsof this invention onto consumer products in different stages such asdamp and dry fabric. Without encapsulation, the free fragrances wouldnormally have evaporated or dissolved in water during use, e.g., wash.Though high logP materials are generally well delivered from a regular(non-encapsulated) fragrance in a consumer product, they have excellentencapsulation properties and are also suitable for encapsulation foroverall fragrance character purposes, very long-lasting fragrancedelivery, or overcoming incompatibility with the consumer product, e.g.,fragrance materials that would otherwise be instable, cause thickeningor discoloration of the product or otherwise negatively affect desiredconsumer product properties.

In some embodiments, the amount of encapsulated active material is from5 to 95% (e.g., 20 to 90% or 40 to 85%) by weight of the microcapsule.The amount of the capsule wall is from 0.5% to 25% (e.g., 1.5 to 15% or2.5 to 10%) also by weight of the microcapsule. In other embodiments,the amount of the encapsulated active material is from 15% to 99.5%(e.g., 50 to 98% or 30 to 95%) by weight of the microcapsule, and theamount of the microcapsule wall is from 0.5% to 85% (e.g., 2 to 50% or 5to 70%) by weight of the microcapsule.

Adjunct Materials.

In addition to the active materials, the present invention alsocontemplates the incorporation of adjunct materials including solvents,emollients, and core modifier materials in the core encapsulated by thecapsule wall. Other adjunct materials are solubility modifiers, densitymodifiers, stabilizers, viscosity modifiers, pH modifiers, or anycombination thereof. These modifiers can be present in the wall or coreof the capsules, or outside the capsules in delivery system. Preferably,they are in the core as a core modifier.

The one or more adjunct material may be added in the amount of from0.01% to 25% (e.g., from 0.5% to 10%) by weight of the capsule.

i) Preferable solvent materials are hydrophobic and miscible with theactive materials. Solvents increase the compatibility of various activematerials, increase the overall hydrophobicity of the mixture containingthe active materials, influence the vapor pressure, or serve tostructure the mixture. Suitable solvents are those having reasonableaffinity for the active materials and a ClogP greater than 2.5,preferably greater than 3.5 and more preferably greater than 5.5. Insome embodiments, the solvent is combined with the active materials thathave ClogP values as set forth above. It should be noted that selectinga solvent and active material with high affinity for each other willresult in improvement in stability. Exemplary solvents are triglycerideoil, mono and diglycerides, mineral oil, silicone oil, diethylphthalate, polyalpha olefins, castor oil, isopropyl myristate, mono-,di- and tri-esters and mixtures thereof, fatty acids, and glycerine. Thefatty acid chain can range from C₄-C₂₆ and can have any level ofunsaturation. For instance, one of the following solvents can be used:capric/caprylic triglyceride known as NEOBEE M5 (Stepan Corporation);the CAPMUL series by Abitec Corporation (e.g., CAPMUL MCM); isopropylmyristate; fatty acid esters of polyglycerol oligomers, e.g.,R²CO—[OCH₂—CH(OCOR¹)—CH²O-]_(n), where R¹ and R² can be H or C₄-C₂₆aliphatic chains, or mixtures thereof, and n ranges between 2 and 50,preferably 2 and 30; nonionic fatty alcohol alkoxylates like the NEODOLsurfactants by BASF; the dobanol surfactants by Shell Corporation or theBIO-SOFT surfactants by Stepan, wherein the alkoxy group is ethoxy,propoxy, butoxy, or mixtures thereof and said surfactants can beend-capped with methyl groups in order to increase their hydrophobicity;di- and tri-fatty acid chain containing nonionic, anionic and cationicsurfactants, and mixtures thereof; fatty acid esters of polyethyleneglycol, polypropylene glycol, and polybutylene glycol, or mixturesthereof; polyalphaolefins such as the EXXONMOBIL PURESYM PAO line;esters such as the EXXONMOBIL PURESYN esters; mineral oil; silicone oilssuch polydimethyl siloxane and polydimethylcyclosiloxane; diethylphthalate; di-octyl adipate and di-isodecyl adipate. In certainembodiments, ester oils have at least one ester group in the molecule.One type of common ester oil useful in the present invention are thefatty acid mono and polyesters such as cetyl octanoate, octylisonanoanate, myristyl lactate, cetyl lactate, isopropyl myristate,myristyl myristate, isopropyl palmitate, isopropyl adipate, butylstearate, decyl oleate, cholesterol isostearate, glycerol monostearate,glycerol distearate, glycerol tristearate, alkyl lactate, alkyl citrateand alkyl tartrate; sucrose ester and polyesters, sorbitol ester, andthe like. A second type of useful ester oil is predominantly composed oftriglycerides and modified triglycerides. These include vegetable oilssuch as jojoba, soybean, canola, sunflower, safflower, rice bran,avocado, almond, olive, sesame, persic, castor, coconut, and mink oils.Synthetic triglycerides can also be employed provided they are liquid atroom temperature. Modified triglycerides include materials such asethoxylated and maleated triglyceride derivatives provided they areliquids. Proprietary ester blends such as those sold by FINETEX asFINSOLV are also suitable, as is ethylhexanoic acid glyceride. A thirdtype of ester oil is liquid polyester formed from the reaction of adicarboxylic acid and a diol. Examples of polyesters suitable for thepresent invention are the polyesters marketed by EXXONMOBIL under thetrade name PURESYN ESTER. While the core can be free of the solvent, itis preferable that the level of solvent is 80 wt % or less, preferably50 wt % or less (e.g., 0-20 wt %) by weight of the core.

ii) Triglycerides and modified triglycerides as emollients. Theseinclude vegetable oils such as jojoba, soybean, canola, sunflower,safflower, rice bran, avocado, almond, olive, sesame, persic, castor,coconut, and mink oils.

iii) Ester oils have at least one ester group in the molecule. One typeof common ester oil useful in the present invention are the fatty acidmono and polyesters such as cetyl octanoate, octyl isonanoanate,myristyl lactate, cetyl lactate, isopropyl myristate, myristylmyristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyloleate, cholesterol isostearate, glycerol monostearate, glyceroldistearate, glycerol tristearate, alkyl lactate, alkyl citrate and alkyltartrate.

iv) Ester oil as a liquid polyester formed from the reaction of adicarboxylic acid and a diol. Examples of polyesters suitable for thepresent invention are the polyesters marketed by ExxonMobil under thetrade name PURESYN ESTER®, hydrophobic plant extracts.

v) Silicones include, for example, linear and cyclicpolydimethylsiloxanes, amino-modified, alkyl, aryl, and alkylarylsilicone oil.

vi) Low/Non Volatile Hydrocarbons

vii) Solid materials. Nanoscale solid particulate materials such asthose disclosed in U.S. Pat. No. 7,833,960 may also be incorporated intothe core and may be selected from, but not limited to, metal or metallicparticles, metal alloys, polymer particles, wax particles, inorganicparticulates, minerals and clay particles. The metal particles can beselected from a non-limiting list of main group elements, transitionmetal and post-transition metal elements including aluminum (Al), silica(Si), Titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), nickel(Ni), cobalt (Co), copper (Cu), gold (Au), silver (Ag), platinum (Pt)and palladium (Pd).

Polymer particles of any chemical composition and nature are suitablefor the present invention as long as their physical dimension falls intothe prescribed region and a liquid core is generated. The polymerparticles can be selected from a nonlimiting list of polymers andco-copolymer based on polystyrene, polyvinyl acetate, polylactides,polyglycolides, ethylene maleic anhydride copolymer, polyethylene,polypropylene, polyamide, polyimide, polycarbonate, polyester,polyurethane, polyurea, cellulose and cellulose, and combinations andmixture of such polymers.

The inorganic particulate can be selected from a non-limiting listincluding silica, titanium dioxide (TiO₂), zinc oxide (ZnO), Fe₂O₃, andother metal oxides such as but not limited to NiO, Al₂O₃, SnO, SnO₂,CeO₂, ZnO, CdO, RuO₂, FeO, CuO, AgO, MnO₂, as well as other transitionmetal oxides.

Examples of nanoscaled material include AEROSIL R812, which has aparticle size of less than 25 nm according to the specification from themanufacture, Degussa Corp. Other suitable materials from Degussainclude, but not limited to, AEROSIL R972, AEROSIL R974, AEROSIL R104,AEROSIL R106, AEROSIL R202, AEROSIL R805, AEROSIL R812, AEROSIL R812S,AEROSIL R816, AEROSIL R7200, AEROSIL R9200, and AEROXIDE TiO2 P25,AEROXIDE T805, AEROXIDE LE1, AEROXIDE LE2, AEROXIDE TiO2 NKT 90,AEROXIDE Alu C805, titanium dioxide PF2, SIPERNAT D110, SIPERNAT D-380.The hydrophobic materials from Deguassa Corp. such as including AEROSILER812 and R972 are especially preferred.

Nanoscaled materials such as UVINUL TiO₂ and Z-COTE HP1 manufactured byBASF can also be used as well as and TI-PURE titanium dioxide, TI-PURER-700, and TI-SELECT. Additional suitable materials include TS-6200 fromDupont and ZEROFREE 516, HUBERDERM 2000 and HUBERDERM 1000 from the J.M.Huber Corporation, Havre De Grace, Md. Silica products such as SYLOID63, 244, 72, 63FP 244FP, 72FP, SYLOX 15, 2 and Zeolites such as SYLOSIVA3, SYLOSIV A4 and SYLOSIV K300 from Grace Davison can also be used.

viii) Polymeric core modifiers. Polymeric core modifiers are alsocontemplated. It has been found that the addition of hydrophobicpolymers to the core can also improve stability by slowing diffusion ofthe fragrance from the core. The level of polymer is normally less than80% of the core by weight, preferably less than 50%, and most preferablyless than 20%. The basic requirement for the polymer is that it bemiscible or compatible with the other components of the core, namely thefragrance and other solvent. Preferably, the polymer also thickens orgels the core, thus further reducing diffusion. Polymeric core modifiersinclude copolymers of ethylene; copolymers of ethylene and vinyl acetate(ELVAX polymers by DOW Corporation); copolymers of ethylene and vinylalcohol (EVAL polymers by Kuraray); ethylene/acrylic elastomers such asVALNAC polymers by Dupont; polyvinyl polymers, such as polyvinylacetate; alkyl-substituted cellulose, such as ethyl cellulose (ETHOCELmade by DOW Corporation) and hydroxypropyl celluloses (KLUCEL polymersby Hercules); cellulose acetate butyrate available from EastmanChemical; polyacrylates (e.g., AMPHOMER, DEMACRYL LT and DERMACRYL 79,made by National Starch and Chemical Company, the AMERHOLD polymers byAmerchol Corporation, and ACUDYNE 258 by ISP Corporation); copolymers ofacrylic or methacrylic acid and fatty esters of acrylic or methacrylicacid such as INTELIMER POLYMERS made by Landec Corporation (see alsoU.S. Pat. No. 4,830,855, U.S. Pat. No. 5,665,822, U.S. Pat. No.5,783,302, U.S. Pat. No. 6,255,367 and U.S. Pat. No. 6,492,462);polypropylene oxide; polybutylene oxide of poly(tetrahydrofuran);polyethylene terephthalate; polyurethanes (DYNAM X by National Starch);alkyl esters of poly(methyl vinyl ether); maleic anhydride copolymers,such as the GANTREZ copolymers and OMNIREZ 2000 by ISP Corporation;carboxylic acid esters of polyamines, e.g., ester-terminated polyamides(ETPA) made by Arizona Chemical Company; polyvinyl pyrrolidone (LUVISKOLseries of BASF); block copolymers of ethylene oxide, propylene oxideand/or butylenes oxide including, e.g., PLURONIC and SYNPERONICpolymers/dispersants by BASF. Another class of polymers includepolyethylene oxide-co-propyleneoxide-co-butylene oxide polymers of anyethylene oxide/propylene oxide/butylene oxide ratio with cationic groupsresulting in a net theoretical positive charge or equal to zero(amphoteric). The general structure is:

where R¹, R², R³, and R⁴ are independently H or any alkyl or fatty alkylchain group. Examples of such polymers are the commercially known asTETRONICS by BASF Corporation.

ix) Sacrificial core ingredients. These ingredients can also be includedin the core and are designed to be lost during or after manufacture andinclude, but are not limited to, highly water soluble or volatilematerials.

x) Solubility modifiers. Nonlimiting examples of a solubility modifierinclude surfactants (e.g., SLS and TWEEN 80), acidic compounds (e.g.,mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, andphosphoric acid, and carboxylic acids such as acetic acid, citric acid,gluconic acid, glucoheptonic acid, and lactic acid), basic compounds(e.g., ammonia, alkali metal and alkaline earth metal hydroxides,primary, secondary, or tertiary amines, and primary, secondary, ortertiary alkanolamines), ethyl alcohol, glycerol, glucose, galactose,inositol, mannitol, glactitol, adonitol, arabitol, and amino acids.

xi) Density modifiers. The density of the capsule slurry and/or the oilcore can be adjusted so that the capsule composition has a substantiallyuniform distribution of the capsules using known density modifiers ortechnologies such as those described in Patent Application PublicationsWO 2000/059616, EP 1502646, and EP 2204155. Suitable density modifiersinclude hydrophobic materials and materials having a desired molecularweight (e.g., higher than about 12,000), such as silicone oils,petrolatums, vegetable oils, especially sunflower oil and rapeseed oil,and hydrophobic solvents having a desired density (e.g., less than about1,000 Kg/m³ at 25° C., such as limonene and octane.

xii) Stabilizers. In some embodiments, a stabilizer (e.g., a colloidalstabilizer) is added to a capsule delivery system to stabilize theemulsion and/or capsule slurry. Examples of colloidal stabilizers arepolyvinyl alcohol, cellulose derivatives such hydroxyethyl cellulose,polyethylene oxide, copolymers of polyethylene oxide and polyethylene orpolypropylene oxide, or copolymers of acrylamide and acrylic acid. Inother embodiments, a stabilizing agent (i.e., a stabilizer) is added tothe capsule delivery system to improve the stability of the deliverysystem for an extended period of storage. When one of these deliverysystem is added to a consumer product such as a liquid fabricsoftener/freshener and liquid detergent, this delivery system will alsoimprove the viscosity stability of the consumer product, thus extend theshelf life of the product.

Useful stabilizing agents include multi-functional amines, aminoacids/peptides, mono-functional amines, polymers, and a polymericmixture. These stabilizing agents are in presence in the compositions asfree compounds, which are not covalently attached to the capsule walls,being part of the capsule walls, or encapsulated in capsules.

Multi-functional amines are those having at least an amine group(primary, secondary, or tertiary) and one or more other functionalgroups such as an amine and hydroxyl group. Exemplary multi-functionalamines include hexamethylenediamine, hexaethylenediamine,ethylenediamine, 1,3-diaminopropane, 1,4-diamino-butane,diethylenetriamine, pentaethylenehexamine, bis(3-aminopropyl)amine,bis(hexan-ethylene)triamine, tris(2-aminoethyl)amine,triethylene-tetramine, N,N′-bis(3-aminopropyl)-1,3-propanediamine,tetraethylenepentamine, amino-2-methyl-1-propanol branchedpolyethylenimine, chitosan, 1,3-diamino-guanidine,1,1-dimethylbiguanide, and guanidine. Suitable amino acids/peptidesinclude arginine, lysine, histidine, ornithine, nisin, and gelatin.Suitable stabilizing polymers include polyvinylpyrrolidone,polyvinylpyridine-N-oxide, and polyvinyl imidazolinium. These polymerssometimes are used in combination with a second polymer (e.g., a blockcopolymer) such that the second polymer.

Monofunational amines have a single amine group. Examples include C₁-C₂₀primary, secondary, or tertiary amines, each of which typically has amolecular weight of 30 to 800 Daltons (e.g., 31 to 500 Daltons and 31 to300 Daltons). They can be linear, branched, cyclic, acyclic, saturated,unsaturated, aliphatic, and/or aromatic. Nonlimiting examples aremethylamine, dimethylamine, trimethylamine, ethylamine, diethylamine,triethylamine, propylamine, isopropylamine, butylamine, dodecylamine,tetradecylamine, aniline, 4-methylaniline, 2-nitroaniline, diphenylamine, pyrrolidone, piperidine, and morpholine.

The stabilizing agent in the capsule composition can be present in anamount effective to stabilize the composition and/or the final consumerproduct containing the composition. This amount can be 1 ppm or greater(e.g., 20 ppm or greater, 20 ppm to 20%, 50 ppm to 10%, 50 ppm to 2%, 50ppm to 1%, 50 to 2000 ppm, and 50 to 1000 ppm). Its concentration in aconsumer product can be 20 ppm to 2% (e.g., 50 ppm to 2%, 50 ppm to 1%,50 to 2000 ppm, or 50 to 1000 ppm).

xiii) Viscosity control agents. Viscosity control agents (e.g.,suspending agents), which may be polymeric or colloidal (e.g., modifiedcellulose polymers such as methylcellulose, hydoxyethylcellulose,hydrophobically modified hydroxyethylcellulose, and cross-linkedacrylate polymers such as Carbomer, hydrophobically modified polyethers)can be included in the capsule core or wall. Optionally, silicas, eitherhydrophobic or hydrophilic, can be included at a concentration fromabout 0.01% to about 20%, more preferable from 0.5% to about 5%, by theweight of the capsule composition. Examples of hydrophobic silicasinclude silanols, surfaces of which are treated with halogen silanes,alkoxysilanes, silazanes, and siloxanes, such as SIPERNAT D17, AEROSILR972 and R974 available from Degussa. Exemplary hydrophilic silicas areAEROSIL 200, SIPERNAT 22S, SIPERNAT 505 (available from Degussa), andSYLOID 244 (available from Grace Davison).

xiv) Humectants. One or more humectants are optionally included to holdwater in the capsule composition for a long period of time. Examplesinclude glycerin, propylene glycol, alkyl phosphate esters, quaternaryamines, inorganic salts (e.g., potassium polymetaphosphate, sodiumchloride, etc.), polyethylene glycols, and the like.

Further suitable humectants, as well as viscosity control/suspendingagents, are disclosed in U.S. Pat. No. 4,428,869, U.S. Pat. No.4,464,271, U.S. Pat. No. 4,446,032, and U.S. Pat. No. 6,930,078. Detailsof hydrophobic silicas as a functional delivery vehicle of activematerials other than a free flow/anticaking agent are disclosed in U.S.Pat. No. 5,500,223 and U.S. Pat. No. 6,608,017.

xv) pH modifiers. In some embodiments, one or more pH modifiers areincluded in the capsule composition to adjust the pH value of thecapsule slurry and/or the capsule cores. The pH modifiers can alsoassist in the formation of capsule walls by changing the reaction rateof the cross-linking reactions that form the capsule walls. Exemplary pHmodifiers include metal hydroxides (e.g., LiOH, NaOH, KOH, and Mg(OH)₂),metal carbonates and bicarbonates (CsCO₃ Li₂CO₃, K₂CO₃, NaHCO₃, andCaCO₃), metal phosphates/hydrogen phosphates/dihydrogen phosphates,metal sulfates, ammonia, mineral acids (HCl, H₂SO₄, H₃PO₄, and HNO₃),carboxylic acids (e.g., acetic acid, citric acid, lactic acid, benzoicacid, and sulfonic acids), and amino acids.

The level of the adjunct materials can be present at a level of 0.01 to25% (e.g., from 0.5% to 10%) or greater than 10% (e.g., greater than 30%and greater than 70%).

Second Deposition Aid.

In addition to the deposition protein of this invention, themicrocapsule can further include a second deposition aid, e.g., one ormore anionically, cationically, nonionically, or amphotericwater-soluble polymers, which is coated on the microcapsules before,during or after coating the microcpasules with the deposition protein.In particular embodiments, the second deposition aid is used incombination with microcapsules coated with a protein-silanol copolymer,protein-silane copolymer, protein-siloxane copolymer, and a combinationthereof. Those skilled in the art would appreciate that the charge ofthese polymers can be adjusted by changing the pH, depending on theproduct in which this technology is to be used. Any suitable method forcoating the deposition aids onto the encapsulated fragrance materialscan be used. The nature of suitable polymers for assisted capsuledelivery to interfaces depends on the compatibility with the capsulewall chemistry since there has to be some association to the capsulewall. This association can be through physical interactions, such ashydrogen bonding, ionic interactions, hydrophobic interactions, electrontransfer interactions or, alternatively, the polymer coating could bechemically (covalently) grafted to the capsule or particle surface.Chemical modification of the capsule or particle surface is another wayto optimize anchoring of the polymer coating to capsule or particlesurface. Furthermore, the capsule and the polymer need to be compatiblewith the chemistry (polarity, for instance) of the desired interface.Therefore, depending on which capsule chemistry and interface (e.g.,cotton, polyester, hair, skin, wool), the second deposition aid can beselected from one or more polymers with an overall zero (amphoteric:mixture of cationic and anionic functional groups) or net positivecharge, based on the following polymer backbones: polysaccharides,polypeptides, polycarbonates, polyesters, polyolefinic (vinyl, acrylic,acrylamide, poly diene), polyester, polyether, polyurethane,polyoxazoline, polyamine, silicone, polyphosphazine, olyaromatic, polyheterocyclic, or polyionene, with molecular weight (MW) ranging fromabout 1,000 to about 1000,000,000, preferably from about 5,000 to about10,000,000. As used herein, molecular weight is provided as weightaverage molecular weight.

Particular examples of cationic polymers that can be used as the seconddeposition aid include, e.g., polysaccharides such as guar, alginates,starch, xanthan, chitosan, cellulose, dextrans, arabic gum, carrageenan,and hyaluronates. These polysaccharides can be employed with cationicmodification and alkoxy-cationic modifications such as cationichydroxyethyl or cationic hydroxypropyl. For example, cationic reagentsof choice are 3-chloro-2-hydroxypropyl trimethylammonium chloride or itsepoxy version. Another example is graft-copolymers of polyDADMAC oncellulose. Alternatively, polysaccharides can be employed with aldehyde,carboxyl, succinate, acetate, alkyl, amide, sulfonate, ethoxy, propoxy,butoxy, and combinations of these functionalities; or any hydrophobicmodification (compared to the polarity of the polysaccharide backbone).The above modifications can be in any ratio and the degree offunctionalization can be up to complete substitution of allfunctionalizable groups, as long as the theoretical net charge of thepolymer is zero (mixture of cationic and anionic functional groups) orpreferably positive. Furthermore, up to five different types offunctional groups may be attached to the polysaccharides. Also, polymergraft chains may be differently modified to the backbone. Thecounterions can be any halide ion or organic counter ion. See U.S. Pat.No. 6,297,203 and U.S. Pat. No. 6,200,554.

Another source of cationic polymers contain protonatable amine groups sothat the overall net charge is zero (amphoteric: mixture of cationic andanionic functional groups) or positive. The pH during use will determinethe overall net charge of the polymer. Examples include unmodified silkprotein, zein, gelatin, keratin, collagen and any polypeptide, such aspolylysine.

Further cationic polymers include polyvinyl polymers with up to fivedifferent types of monomers can be used. The monomers of such polymerhave the generic formula:

—C(R²)(R¹)—CR²R³—

wherein, R¹ is H, C₁-C₂₅ alkane, C₁-C₂₅ alkene (in which the number ofdouble bonds ranges from 1-5), C₁-C₂₅ alkoxylated fatty alcohol, or aliquid crystalline moiety that can provide the polymer with thermotropicliquid crystalline properties; R² is H or CH₃; and R³ is —Cl, —NH₂(i.e., polyvinyl amine or its copolymers with N-vinyl formamide.

Such polyvinyl polymers are sold under the name LUPAMIN 9095 by BASFCorporation. Further suitable cationic polymers containinghydroxylalkylvinylamine units, as disclosed in U.S. Pat. No. 6,057,404.

Another class of materials of use as second deposition aids arepolyacrylates with up to five different types of monomers. Monomers ofpolyacrylates have the generic formula:

—CH(R¹)—C(R²)(CO—R³—R⁴)—

wherein, R¹ is H, C₁-C₂₅ alkane, C₁-C₂₅ alkene (in which the number ofdouble bonds ranges from 1-5), C₁-C₂₅ alkoxylated fatty alcohol, or aliquid crystalline moiety that can provide the polymer with thermotropicliquid crystalline properties; R² is H or CH₃; R³ is a C₁-C₂₅ alkylalcohol or an alkylene oxide with any number of double bonds, or R³ maybe absent such that the C═O bond is (via the C-atom) directly connectedto R⁴; and R⁴ is —NH₂, —NHR¹, —NR¹R², —NR¹R²R⁵ (where R⁵═R¹, R², or—CH₂—COOH or its salt), —NH—C(O)—, sulfobetaine, betaine, polyethyleneoxide, poly(ethyleneoxide/propylene oxide/butylene oxide) grafts withany end group, H, OH, styrene sulfonate, pyridine, quaternized pyridine,alkyl-substituted pyrrolidone or pyridine, pyridine-N-oxide,imidazolinium halide, imidazolium halide, imidazol, piperidine, —OR¹,—OH, —COOH alkali salt, sulfonate, ethoxy sulphate, pyrrolidone,caprolactam, phenyl-R⁴ or naphthalene-R⁶, where R⁴ and R⁶ are R¹, R²,R³, sulfonic acid or its alkali salt or organic counter ion. Also,glyoxylated cationic polyacrylamides can be used. Typical polymers ofchoice are those containing the cationic monomer dimethylaminoethylmethacrylate (DMAEMA) or methacrylamidopropyl trimethyl ammoniumchloride (MAPTAC). DMAEMA can be found in GAFQUAT and GAFFIX VC-713polymers from ISP. MAPTAC can be found in BASF's LUVIQUAT PQ11 PN andISP's GAFQUAT HS100.

Another group of polymers that can be used are those that containcationic groups in the main chain or backbone. Included in this groupare:

i) polyalkylene imines such as polyethylene imine, commerciallyavailable as LUPASOL from BASF. Any molecular weight and any degree ofcrosslinking of this polymer can be used in the present invention;

ii) ionenes as disclosed in U.S. Pat. No. 4,395,541 and U.S. Pat. No.4,597,962;

iii) adipic acid/dimethyl amino hydroxypropyl diethylene triaminecopolymers, such as CARTARETIN F-4 and F-23, commercially available fromSandoz;

iv) polymers of the general formula:—[N(CH₃)₂—(CH₂)_(x)—NH—(CO)—NH—(CH₂)_(y)—N(CH₃)₂)—(CH₂)_(z)—O—(—(CH₂)_(p)]_(n)—,with x, y, z, p=1-12, and n according to the molecular weightrequirements. Examples are Polyquaternium-2 (MIRAPOL A-15),Polyquaternium-17 (MIRAPOL AD-1), and Polyquaternium-18 (MIRAPOL AZ-1).Other polymers include cationic polysiloxanes and cationic polysiloxaneswith carbon-based grafts with a net theoretical positive charge or equalto zero (mixture of cationic and anionic functional groups). Thisincludes cationic end-group functionalized silicones (i.e.,Polyquaternium-80). Silicones with general structure:—Si(R¹)(R²)—O—]_(x)—[Si(R³)(R²)—O—]_(y)— where R¹ is any alkane fromC₁-C₂₅ or H with number of double bonds from 0-5, aromatic moieties,polysiloxane grafts, or mixtures thereof. R¹ can also be a liquidcrystalline moiety that can provide the polymer with thermotropic liquidcrystalline properties. R² can be H or CH₃; and R³ can be —R¹-R⁴, whereR⁴ can be —NH₂, —NHR¹, —NR¹R², —NR¹R²R⁵ (where R₅═R₁, R₂, or —CH₂—COOHor its salt), —NH—C(O)—, —COOH, —COO— alkali salt, any C₁-C₂₅ alcohol,—C(O)—NH₂ (amide), —C(O)—N(R²)(R^(2′),)(R^(2″)) sulfobetaine, betaine,polyethylene oxide, poly(ethyleneoxide/propylene oxide/butylene oxide)grafts with any end group, H, —OH, styrene sulfonate, pyridine,quaternized pyridine, alkyl-substituted pyrrolidone or pyridine,pyridine-N-oxide, imidazolinium halide, imidazolium halide, imidazol,piperidine, pyrrolidone, caprolactam, sulfonate, ethoxysulphatephenyl-R⁶ or naphthalene-R⁷ where R⁶ and R⁷ are R¹, R², R³, sulfonicacid or its alkali salt or organic counter ion. R³ can also be—(CH₂)_(x)—O—CH₂—CH(OH)—CH₂—N(CH₃)₂—CH₂—COOH and its salts. Any mixtureof these R³ groups can be selected. X and y can be varied as long as thetheoretical net charge of the polymer is zero (amphoteric) or positive.In addition, polysiloxanes containing up to five different types ofmonomeric units may be used. Examples of suitable polysiloxanes arefound in U.S. Pat. Nos. 4,395,541 4,597,962 and U.S. Pat. No. 6,200,554.Another group of polymers that can be used to improve capsule/particledeposition are phospholipids that are modified with cationicpolysiloxanes. Examples of these polymers are found in U.S. Pat. No.5,849,313, WO 1995/18096A1 and EP 0737183B1.

Another class of polymers includes polyethyleneoxide-co-propyleneoxide-co-butylene oxide polymers of any ethyleneoxide/propylene oxide/butylene oxide ratio with cationic groupsresulting in a net theoretical positive charge or equal to zero(amphoteric). Examples of such polymers are the commercially availableTETRONIC brand polymers.

Suitable polyheterocyclic (the different molecules appearing in thebackbone) polymers include the piperazine-alkylene main chain copolymersdisclosed by Kashiki & Suzuki (1986) Ind. Eng. Chem. Fundam. 25:120-125.

Table 2 below shows polyquaternium polymers that can be used asdeposition aids in this invention.

TABLE 2 Poly- quaternium Description Commercial Product 1 Ethanol,2,2′,2″-nitrilotris-, polymer POLYQUAD (Alcon) with1,4-dichloro-2-butene and N,N,N′,N′-tetramethyl-2-butene-1,4- diamine 2Poly[bis(2-chloroethyl) ether-alt-1,3- MIRAPOL A-15bis[3-(dimethylamino)propyl]urea] 4 Hydroxyethyl cellulose dimethylCELQUAT L-200, H-100, diallylammonium chloride copolymer; L-200Diallyldimethylammonium chloride- hydroxyethyl cellulose copolymer 5Copolymer of acrylamide and MERQUAT 5, RETEN quaternizeddimethylammoniumethyl (Hercules) methacrylate 6 Poly(diallyldimethylammonium MERQUAT 100, 106, chloride) MIRAPOL 100 7 Copolymer ofacrylamide and MERQUAT 550, 550L, diallyldimethylammonium chloride550PR, S, 7SPR, 740, 2200, MIRAPOL 550, POLYQUART 770/NA, CONDITIONEZE 78 Methyl and Stearyl Dimethylaminoethyl Methacrylate Quaternized withDimethyl Sulfate 9 Polydimethylaminoethyl Methacrylate Quaternized withMethyl Bromide 10 Quaternized hydroxyethyl cellulose MERQUAT 10, CELQUATSC-230M, SC-240C, SC-140C, UCARE Polymer 11 Copolymer ofvinylpyrrolidone and LUVIQUAT PQ 11PN, quaternized dimethylaminoethylGAFQUAT 775N, 440, methacrylate 734, 775 12 2-Propenoic Acid, 2-Methyl-,Decahydro-1,4-Dimethyl-7-(1- Methylethyl)-1-Phenanthrenyl)Methyl Ester,Polymer with 2- (Diethylamino)Ethyl 2-Methyl-2- Propenoate and Ethyl2-Methyl-2- Propenoate, compd. with Dimethyl Sulfate 13 2-PropenoicAcid, 2-Methyl-, 2- (Diethyl-amino)Ethyl Ester, Polymer with Ethyl2-Methyl-2-Propenoate and 9-Octadecenyl 2-Methyl-2-Propenoate, compd.with Dimethyl Sulfate 14 Ethanaminium, N,N,N-Trimethyl-2-[(2-Methyl-1-Oxo-2-Propenyl)Oxy]-, Methyl Sulfate, Homopolymer 15Ethanaminium, N,N,N-Trimethyl-2-[(2- ROHAGIT KF 720FMethyl-1-Oxo-2-Propenyl)Oxy]-, (Rohm GmbH) Chloride, Polymer with2-Propenamide 16 Copolymer of vinylpyrrolidone and LUVIQUAT FC 370, HMquaternized vinylimidazole 552, Style, FC 550, Excellence 17Poly(Oxy-1,2-Ethanediyl (Dimethyl- MIRAPOL ADiminio)-1,3-Propanediylimino(1,6- Dioxo-1,6-Hexanediyl)Imino-1,3-Propanediyl-(Dimethyliminio)-1,2- Ethanediyl Dichloride 18 Poly[oxy-1,2-LUVIQUAT 500 ethanediyl(dimethyliminio)-1,3-propanediylimino-(1,6-dioxo-1,6- heptanediyl)imino-1,3-propanediyl-(dimethyliminio)-1,2-ethanediyl dichloride] 19 Ethenol, polymer withARLATONE PQ-220 (ICI aminomethyloxirane Americas) 20 Ethenyl octadecylether, polymer with ARLATONE PQ-225 aminomethyloxirane 22 Copolymer ofAcrylic Acid and MERQUAT 280, 281, Diallyldimethylammonium Chloride280SD, 295 24 Cellulose, 2-[2-Hydroxy-3-(Trimethyl- QUATRISOFT Polymerammonio)Propoxy]Ethyl Ether, LM-200 (Dow Chemical) Chloride (Similar toPQ-10) 27 Hexanediamide, N,N′-bis(3-(Dimethyl- amino)Propyl)-, Polymerwith N,N′- bis(3- Dimethylamino)Propyl Urea and 1,1′-Oxybis(2-Chloroethane), Block 28 Copolymer of vinylpyrrolidone andGAFQUAT HS-100, meth-acrylamidopropyl CONDITIONEZE NT-10trimethylammonium 29 Chitosan, 2,3-Dihydroxypropyl-2- QuaternizedChitosan Hydroxy-3-(Trimethylammonio)Propyl Ether, Chloride 30Ethanaminium, NCarboxymethyl)-N,N- MEXOMERE PXDimethyl-2-((2-Methyl-1-Oxo-2- (Chimex) Propenyl)Oxy)-, Inner Salt,Polymer with Methyl 2-Methyl-2-Propenoate 31 2-Propenenitrile,Homopolymer, HYPAN QT100 (Lipo) Hydrolyzed, Block, Reaction Productswith N,N-Dimethyl-1,3- Propanediamine, Di-Et Sulfate- Quaternized 32Poly(acrylamide 2-methacryloxyethyl- COSMEDIA CTC trimethyl ammoniumchloride) (Cognis GmbH) - PQ-32 + other, SALCARE SC92 (Ciba Corp.)PQ-32 + other 33 Ethanaminium, N,N,N-Trimethyl-2-[1- LANOQUAT DES-50,Oxo-2-Propenyl)Oxy]-, Chloride, ULTIMER CG-200 Polymer with2-Propenamide (Nalco), SEPIGEL Quat33 (Seppic) - PQ-33 + other 34Poly(diethyliminio-1,3-propanediyldimethyliminio- MEXOMERE PAK1,3-propanediyl (Chimex) dibromide) 35 Ethanaminium,N-carboxymethyl-N,N- PLEX 3074 L (Rohm dimethyl-2-(2-methyl-1-oxo-2-GmbH) propenyloxy)-, inner salt, polymer withN,N,N-trimethyl-2-(2-methyl-1-oxo-2- propenyloxy)ethanaminium methylsulfate 36 2-Propenoic Acid, 2-Methyl-,2- PLEX 4739L (Rohm(Dimethylamino)Ethyl Ester, Polymer GmbH) with Methyl2-Methyl-2-Propenoate, compd. with Dimethyl Sulfate 37N,N,N-Trimethyl-2-[(Methyl-1-Oxo-2- ULTRAGEL 300Propenyl)Oxy]Ethanaminium Chloride, (Cognis), SYNTHALEN Homopolymer CN,CR, CU (3V Group), SYNTRAN PC 5320 (Interpolymer) 39 2-Propen-1-aminium,N,NDimethyl-N- MERQUAT 3940, PLUS- 2-Propenyl-, Chloride, Polymer with2- 3330, PLUS-3331, Propenamide and 2-Propenoic Acid 3331PR 42Poly[oxyethylene(dimethyliminio)ethylene- BUSAN 1507 (Buckman(dimethylimino)ethylene dichloride] Labs) 43 polymeric quaternaryammonium salt GENAMIN PQ 43 formed from acrylamide, (Clariantacrylamidopropyltrimonium chloride, 2- Functional Chemicals),amidopropylacrylamide sulfonate, and BOZEQUAT 4000 DMAPA monomers(Clariant) 44 Poly(2-oxopyrrolidin-1-ylethylene, 3- LUVIQUATmethylimidazolium-1-ylethylene methyl ULTRACARE, MS 370 sulfate) (BASF),SOFTENOL PQ44 (Zdchimmer & Schwarz Italianat S.p.A) 45 Glycine,N-methyl-N-[2-[(2-methyl-1- PLEX 3073L (Rohm oxo-2-propenyl)oxy]ethyl]-,polymer GmbH) with 2-(dimethylamino)ethyl 2-methyl- 2-propenoate,compound with dimethyl sulfate 46 1H-Imidazolium, 1-Ethenyl-3-Methyl-,LUVIQUAT Hold Methyl Sulfate, Polymer with 1-Ethenyl-hexahydro-2H-Azepin-2-one and 1-Ethenyl-2-Pyrrolildinone 471-Propanaminium, N,N,NTrimethyl-3- MERQUAT 2001, 2001N((2-Methyl-1-Oxo-2-Propenyl)Amino)- Chloride, Polymer with Methyl 2-Propenoate and 2-Propenoic Acid 48 Polymeric quaternary ammonium salt ofPLASCIZE L-450 (Goo formed from methacryloyl ethyl betaine, Chemical)2-hydroxyethyl methacrylate and methacryloyl ethyl trimethyl ammoniumchloride 49 polymeric quaternary ammonium salt PLASCIZE L-440 formed bythe reaction of methacryloyl (Goo Chemical) ethyl betaine, PEG-9methacrylate and methacryloyl ethyl trimethyl ammonium chloride 50Carboxylatoethyldimethylammonioethyl PLASCIZE L-401 (Goo2-methyl-2-propenoate homopolymer Chemical) 513,5,8-Triox-4-Phosphaundec-10-en-1- LIPIDURE PMB aminium,4-Hydroxy-N,N,N,10- (NOF) Tetramethyl-9-Oxo, Inner Salt, 4-Oxide,Polymer with Butyl 2-Methyl-2- Propenoate 53 AcrylicAcid/Acrylamide/Methacryl- MERQUAT 2003PR amidopropyltrimonium ChlorideCopolymer 54 Aspartic acid, polymer with C6-18 Quilty-Hy (Mitsui)alkylamine, 3- dimethylaminopropylamine and sodium chloroacetate 551-Dodecanaminium, N,NDimethyl-N- STYREZE W[3-[(2-Methyl-1-Oxo-2-Propenyl)- Amino-Propyl]-, Chloride, Polymer withN-[3-(Dimethylamino)Propyl]-2- Methyl-2-Propenamide and 1-Ethenyl-2-Pyrrolidinone 56 5-Isocyanato-1-(isocyanatomethyl)- HAIRROL UC-4(Sanyo 1,3,3-trimethylcyclohexane, polymer Chemical) with 1,3-butanedioland bis(2- hydroxyethyl)di-methylammonium methyl sulfate 5712-Hydroxy-9(Z)- ZENIGLOSS Q octadecenamidopropyl- (Zenitech)trimethylammonium chloride, polymers with ricinus communis (castor) oil,isooctdecanoic acid and butandioic acid 58 2-Propenoic Acid, MethylEster, LOWENOL Conditioner Polymer with 2,2-Bis[(2- PWWPropenyloxy)Methyl]-1-Butanol and (Lowenstein) - PQ-58 andDiethenylbenzene, Reaction Products Wheat Protein withN,N-Dimethyl-1,3-Propane- diamine, Chloromethane-Quaternized 59Poly(20,25-dioxo-2,5,10,15,18-penta- CRODASORB UV-HPPmethyl-10-(2-hydroxy-3-(3-(3-phenyl-2- (Croda, Inc.) - PQ-59 andpropenamido)propyldimethylammonio)propyl)- Butylene Glycol10-azonia-1,4,7,13,16,19- hexaoxa-pentacosanediyl) chloride 609-Octadecenoic Acid, 12-Hydroxy-, [(2- Polylipid PPI-RCHydroxyethyl)-Imino]Di-2,1-Ethanediyl (Alzo/Bernel) - PQ-60 Ester,Polymer with 5-Isocyanato-1- and Propylene Glycol(Isocyanatomethyl)-1,3,3-Trimethyl- cyclohexane, Compd. with DiethylSulfate 61 2-Methyl-2-propenoyloxyethyl N,N,N- LIPIDURE-S (NOF)trimethylammonioethyl phosphate inner salt, polymer with octadecyl2-methyl-2- propenoate 62 Polymeric quaternary ammonium salt ofNANOAQUASOME butyl methacrylate, polyethylene glycol (AmorePacific/Kyung- methyl ether methacrylate, ethylene do) glycoldimethacrylate and 2- methacryloylethyl trimonium chloride with2,2′-azobis(2-methyl propionamidine)dihydro-chloride 63 polymericquaternary ammonium salt FINQUAT (Innospec), formed by acrylamide,acrylic acid and OCTACARE PQ63 ethyltrimonium chloride acrylate(Innospec Edison, NJ), OF-308 (WSP Chemical & Technology) 642-Methyl-2-propenoyloxyethyl N,N,N- LIPIDURE-C (NOF)trimethylammonioethyl phosphate inner salt, polymer with 2-hydroxy-3-(2-methyl-2- propenoyl)oxypropyltrimethyl- ammonium chloride 652-Methyl-2-propenoyloxyethyl N,N,N- LIPIDURE-A (NOF)trimethylammonioethyl phosphate inner salt, polymer with butyl2-methyl-2- propenoate and sodium 2-methyl-2- propenoate 665-Isocyanato-1-(isocyanatomethyl)- WBR-2925C (Taisei) -1,3,3-trimethylcyclohexane, polymer PQ-66 and Methyl withdi(hydroxypolymethylene) Pyrrolidone benzene-dicarboxylate andethylbis(2- hydroxy-ethyl)methylammonium ethyl sulfate 67 2-Hydroxyethylcellulose ether, reaction SOFTCAT (Dow products with N,N,N-trimethyl-N-Chemical) oxiranylmethylammonium chloride and N-dodecyl-N,N-dimethyl-N-oxiranylmethylammonium chloride 68 1-Ethenyl-2-pyrrolidinone, polymerLUVIQUAT Supreme with 1-ethenylimidazole and 1-ethenyl-3-methylimidazolium methyl sulfate 69 polymeric quaternary ammonium saltAQUASTYLE 100, 300 composed of vinyl caprolactam, (ISP)vinylpyrrolidone, dimethylaminopropyl methacrylamide (DMAPA), andmethacryloylaminopropyl lauryldimonium chloride 70 polymeric quaternaryammonium salt LUSTREPLEX (Croda) consisting of an ethoxylated,propoxylated stearyl amine condensed with adipic acid and dilinoleicacid and quaternized with dimethyl sulfate 71 COLAMOIST 300P (ColonialChemical Inc) 72 polymeric quaternary ammonium salt of MIRUSTYLE CP(Croda) hydroxethylcellulose reacted with a coco-alkyl dimethyl ammoniumsubstituted epoxide 73 polymeric quaternary ammonium salt DIAFORMERC-802, C- consisting of propyltrimonium chloride 823 (Mitsubishi Chem),acrylamide, ethyltrimonium chloride DIASLEEK C-802, C-823 methacrylateand dimethylacrylamide (Mitsubishi Chem) monomers; Propanaminium, N,N,N-trimethyl-3-(2-propenamido)-, chloride, polymer withN,N,N-trimethyl-2-(2- methyl-2-propenoyloxy)ethanaminium chloride andN,N-dimethyl-2- propenamide 74 MIRAPOL PB 20 (Rhodia) POLYCARE Boost(Rhodia) 75 O-(2-Hydroxy-2-trimethylammonio- AMYLOMER Cat propyl)starchchloride, reaction products 220EMU (Grafe Chemie) withO-(3-dodecyldimethylammonio-2- hydroxypropyl)starch chloride 76 MirapolAT-1 (Rhodia) 77 Cocoglucoside Crosspolymer Colonial Poly SugaQuatHydroxypropyltrimonium Chloride TM-8610P (Colonial Chemical Inc) 78Decylglucoside Crosspolymer Colonial POLY SUGA HydroxypropylLaurdimonium Chloride Quat L-1010P (Colonial Chemical Inc) 79Decylglucoside Crosspolymer Colonial POLY SUGA HydroxypropylSteardimonium Chloride Quat S-1010P (Colonial Chemical Inc) 80Laurylglucoside Crosspolymer Colonial POLY SUGA HydroxypropylLaurdimonium Chloride Quat L-1210P (Colonial Chemical Inc) 81Laurylglucoside Crosspolymer Colonial POLY SUGA HydroxypropylSteardimonium Chloride Quat S-1210P (Colonial Chemical Inc) 82Laurylglucoside Crosspolymer Colonial P POLY SUGA HydroxypropyltrimoniumChloride Quat TM-1218P (Colonial Chemical Inc) 84 polymeric quaternaryammonium salt of DIASLEEK C-824 acrylamidopropyltrimethyl-ammonium(Mitsubishi Chemical) chloride, trimethylaminoethyl methacrylate,dimethylacrylamide and hydroxyethylmethacrylate 85 polymeric quaternaryammonium salt of DIASLEEK C-825 acrylamidopropyltrimethyl-ammonium(Mitsubishi Chemical) chloride, dimethylacrylamide andhydroxyethylmethacrylate 86 polymeric quaternary ammonium salt ofLUVIGEL Advanced vinylpyrrolidone, 1-methyl-3- (BASF) vinylimidazolinechloride, vinylimidazole and methacrylic acid 87 polymeric quaternaryammonium salt of LUVIQUAT Sensation vinylpyrrolidone, vinylimidazole and(BASF) diallyldimethyl ammonium chloride 88 Poly(DilinoleyldimoniumCOLAQUAT PDQ hydroxypropyl)chlorides) (Colonial Chemical Inc) 89polymeric quaternary ammonium salt (BASF) prepared by the reaction oft-butyl acrylate, vinyl pyrolidone, dimethylaminopropyl methacrylamide,methacrylic acid and ethyldimethyl[2- [(2-methyl-1-oxoally)oxy]ammoniumethyl sulfate, neutralized with orthophosphoric acid 90 polymericquaternary ammonium salt of HYMOQUAT AK325R acrylamide andhydroxyethylcellulose (Hymo Corporation) quaternized withdiallyldimethyl ammonium chloride 91 polymeric quaternary ammonium saltof SYNTRAN 5500 hydroxypropyl methacrylate and (Interpolymer) - PQ-91polyethylene glycol methacrylate and PA quaternized with ethyltrimoniumchloride methacrylate 92 Glycerylamidoethyl CERACUTE-G (NOF)Methacrylate/Stearyl Methacrylate Copolymer 94 polymeric quaternaryammonium salt (Toho) consisting of acrylamide, dimethyl diallyl ammoniumchloride and methacrylamidopropyltrimonium chloride monomers 95copolymer of Zea Mays (Com) Starch, POLYQUART Ecoclean Acrylic Acid andacrylamidopropyl (Cognis) trimethylammonium chloride monomers 98 (CognisGmbH) 101 DEPOSILK Q1 (Air Products)

Other suitable second deposition aids include those described in US2013/0330292, US 2013/0337023, US 2014/0017278.

The microcapsule composition of this inveniton is prepared by (a)providing a microcapsule slurry having a plurality of microcapsules eachcontaining a polymeric wall and an active material encapsulated withinthe polymeric wall; and (b) curing the microcapsules and coating each ofthe microcapsules with a deposition protein. In some embodiments, themicrocapsules are coated before, during and/or after curing thecapsules. Cure and/or coating temperatures can be in the range of 0 to250° C., 20 to 120° C. or 35 to 75° C. In embodiments where thedeposition protein is a protein-silanol copolymer, a protein-silanecopolymer, a protein-siloxane copolymer, or a combination thereof, it ispreferable that the microcapsules are coated at a temperature between 35to 75° C. before, during or after curing the microcapsules.

Higher performance of the microcapsules can be achieved by curing at ahigher temperature for a longer time. Therefore, in some embodiments,the cross-linked network of polymers containing active materials may becured for periods of up to 1 hour and more preferably longer than twohours. More preferably, the curing period of the capsule is at least upto about 2 hours, at least up to 3 hours or at least up to 4 hours.

In some embodiments, greater performance of the microcapsules can beachieved when the heating profile to the target cure temperature of thecross-linked network of polymers containing the active material ispreferably linear with a heating rate at least up to about 2.0° C. aminute, more preferably at least up to about 5.0° C. a minute, even morepreferably at least up to about 8.0° C. a minute and most preferably atleast up to about 10° C. a minute over a period of time less than aboutsixty minutes and more preferably less than thirty minutes. Thefollowing heating methods may be used in the practice of the presentinvention, conduction for example via oil, steam radiation via infrared,and microwave, convection via heated air, steam injection and othermethods known by those skilled in the art.

In certain embodiments, the deposition protein is cross-linked on thesurface of the microcapsules. In embodiments pertaining to cationicallymodified deposition proteins, the deposition protein can be cross-linkedusing a transglutaminase (EC 2.3.2.13), an enzyme capable of catalyzingacyl transfer reactions introducing covalent cross-links betweenproteins as well as proteins and peptides and primary amines.Transglutaminase can be obtained from several plant, animal or microbialsources. See, e.g., Zhu, et al. (1995) Appl. Microbiol. Biolechnol.44:277-282 and EP 1068301. Alternatively, a conventional proteincross-linking agent such as glutaraldehyde can be used. As a furtheralternative, genipin (Methyl(1R,2R,6S)-2-hydroxy-9-(hydroxymethyl)-3-oxabicyclo[4.3.0]nona-4,8-diene-5-carboxylate),an aglycone derived from an iridoid glycoside called geniposide presentin fruit of Gardenia jasminoides, has been used to cross-link moleculescontaining free amino groups in proteins such as fibrin. See, e.g., US2013/0345321. In particular embodiments, a transglutamase is used tocross-link cationically modified deposition proteins.

In embodiments pertaining to protein-silicon copolymers, the depositionprotein can be cross-linked by adding an alkoxysilane. Suitablealkoxysilane cross-linking agents can have the structure R¹_(X)Si(OR²)_(4-x), wherein x is 0 or 1; and R¹ is an optionallysubstituted C₁-C₈ alkyl, C₆-C₁₄ aryl or C₂-C₈ alkenyl group; and R² isan optionally substituted linear or branched C₁-C₈ alkyl, or C₂-C₈alkoxyalkyl group, wherein R¹ and R² can be the same or different withinthe molecule. Exemplary alkoxysilanes are tetraethoxysilane,tetra-n-propoxysilane, methyltriethoxysilane, methyltrimethoxysilane,methyl tri(2-methoxyethoxy)silane, vinyl trimethoxysilane orvinyltriethoxysilane.

Once prepared, the microcapsule composition can be a slurry in a solvent(e.g., water), wherein the microcapsule are at a level of 0.1 to 80%(preferably 1 to 65% and more preferably 5 to 45%) by weight of themicrocapsule composition.

In some embodiments, the microcapsule composition is subsequentlypurified. Purification can be achieved by washing the capsule slurrywith water, e.g., deionized or double deionized water, until a neutralpH is achieved. For the purposes of the present invention, themicrocapsule suspension can be washed using any conventional methodincluding the use of a separatory funnel, filter paper, centrifugationand the like. The microcapsule suspension can be washed one, two, three,four, five, six, or more times until a neutral pH, e.g., pH 6-8 and6.5-7.5, is achieved. The pH of the purified microcapsule can bedetermined using any conventional method including, but not limited topH paper, pH indicators, or a pH meter.

A microcapsule composition of this invention is “purified” in that it is80%, 90%, 95%, 97%, 98% or 99% homogeneous to microcapsules. Inaccordance with the present invention, purity is achieved by washing themicrocapsules until a neutral pH is achieved, which is indicative ofremoval of unwanted impurities and/or starting materials, e.g.,polyisocyanate, cross-linking agent and the like.

In certain embodiments of this invention, the purification of themicrocapsules includes the additional step of adding a salt to themicrocapsules prior to the step of washing the microcapsule suspensionwith water. Exemplary salts of use in this step of the inventioninclude, but are not limited to, sodium chloride, potassium chloride orbi-sulphite salts. See US 2014/0017287.

Applications.

The microcapsule composition of this invention can be formulated for usein consumer products, in particular rinse-off consumer productapplications such as shampoo, hair conditioner, body wash, detergent,softener, bar soap, scent booster, or hard surface cleaner. Themicrocapsule composition can also contain one or more other microcapsulecompositions such as polymer-assisted delivery compositions (see U.S.Pat. No. 8,187,580), fiber-assisted delivery compositions (US2010/0305021), cyclodextrin host guest complexes (U.S. Pat. No.6,287,603 and US 2002/0019369), pro-fragrances (WO 2000/072816 and EP 0922 084), and any combination thereof. The microcapsule composition canalso contain one or more (e.g., two, three, four, five or six more)different capsules including different capsules of this invention andother capsules such as such as aminoplasts, hydrogel, sol-gel,coascervate capsules, polyurea/polyurethane capsules, and melamineformaldehyde capsules. Further, the microcapsule composition can becombined with free active material.

The microcapsule composition of the present invention are well-suitedfor use, without limitation, in one or more of the following products:

Household products such as liquid or powder laundry detergents includingthose systems described in U.S. Pat. No. 5,929,022, U.S. Pat. No.5,916,862, U.S. Pat. No. 5,731,278, U.S. Pat. No. 5,565,145, U.S. Pat.No. 5,470,507, U.S. Pat. No. 5,466,802, U.S. Pat. No. 5,460,752, U.S.Pat. No. 5,458,810, U.S. Pat. No. 5,458,809, U.S. Pat. No. 5,288,431,U.S. Pat. No. 5,194,639, U.S. Pat. No. 4,968,451, U.S. Pat. No.4,597,898, U.S. Pat. No. 4,561,998, U.S. Pat. No. 4,550,862, U.S. Pat.No. 4,537,707, U.S. Pat. No. 4,537,706, U.S. Pat. No. 4,515,705, U.S.Pat. No. 4,446,042, and U.S. Pat. No. 4,318,818.

Unit dose pouches, tablets and capsules such as those described in EP1431382, US 2013/0219996, US 2013/0284637, and U.S. Pat. No. 6,492,315.These unit dose formulations can contain high concentrations of afunctional material (e.g., 5-100% fabric softening agent or detergentactive), fragrance (e.g., 0.5-100%, 0.5-40%, and 0.5-15%), and flavor(e.g., 0.1-100%, 0.1-40%, and 1-20%). They can contain no water to limitthe water content as low as less than 30% (e.g., less than 20%, lessthan 10%, and less than 5%).

Scent boosters such as those described in U.S. Pat. No. 7,867,968, U.S.Pat. No. 7,871,976, U.S. Pat. No. 8,333,289, US 2007/0269651, and US2014/0107010.

Fabric care products such as rinse conditioners (containing 1 to 30weight % of a fabric conditioning active), fabric liquid conditioners(containing 1 to 30 weight % of a fabric conditioning active), tumbledrier sheets, fabric refreshers, fabric refresher sprays, ironingliquids, and fabric softener systems such as those described in U.S.Pat. No. 6,335,315, U.S. Pat. No. 5,674,832, U.S. Pat. No. 5,759,990,U.S. Pat. No. 5,877,145, U.S. Pat. No. 5,574,179, U.S. Pat. No.5,562,849, U.S. Pat. No. 5,545,350, U.S. Pat. No. 5,545,340, U.S. Pat.No. 5,411,671, U.S. Pat. No. 5,403,499, U.S. Pat. No. 5,288,417, U.S.Pat. No. 4,767,547 and U.S. Pat. No. 4,424,134

Liquid fabric softeners/fresheners contain at least one fabric softeningagent present, preferably at a concentration of 1 to 30% (e.g., 4 to20%, 4 to 10%, and 8 to 15%). The ratio between the active material andthe fabric softening agent can be 1:500 to 1:2 (e.g., 1:250 to 1:4 and1:100 to 1:8). As an illustration, when the fabric softening agent is 5%by weight of the fabric softener, the active material is 0.01 to 2.5%,preferably 0.02 to 1.25% and more preferably 0.1 to 0.63%. As anotherexample, when the fabric softening agent is 20% by weight of the fabricsoftener, the active material is 0.04 to 10%, preferably 0.08 to 5% andmore preferably 0.4 to 2.5%. The active material is a fragrance, malodorcounteractant or mixture thereof. The liquid fabric softener can have0.15 to 15% of capsules (e.g., 0.5 to 10%, 0.7 to 5%, and 1 to 3%). Whenincluding capsules at these levels, the neat oil equivalent (NOE) in thesoftener is 0.05 to 5% (e.g., 0.15 to 3.2%, 0.25 to 2%, and 0.3 to 1%).

Suitable fabric softening agents include cationic surfactants.Non-limiting examples are quaternary ammonium compounds such asalkylated quaternary ammonium compounds, ring or cyclic quaternaryammonium compounds, aromatic quaternary ammonium compounds, diquaternaryammonium compounds, alkoxylated quaternary ammonium compounds,amidoamine quaternary ammonium compounds, ester quaternary ammoniumcompounds, and mixtures thereof. Fabric softening compositions, andcomponents thereof, are generally described in US 2004/0204337 and US2003/0060390. Suitable softening agents include esterquats such asREWOQUAT WE 18 commercially available from Evonik Industries andSTEPANTEX SP-90 commercially available from Stepan Company.

Liquid dish detergents such as those described in U.S. Pat. No.6,069,122 and U.S. Pat. No. 5,990,065. Automatic Dish Detergents such asthose described in U.S. Pat. No. 6,020,294, U.S. Pat. No. 6,017,871,U.S. Pat. No. 5,968,881, U.S. Pat. No. 5,962,386, U.S. Pat. No.5,939,373, U.S. Pat. No. 5,914,307, U.S. Pat. No. 5,902,781, U.S. Pat.No. 5,705,464, U.S. Pat. No. 5,703,034, U.S. Pat. No. 5,703,030, U.S.Pat. No. 5,679,630, U.S. Pat. No. 5,597,936, U.S. Pat. No. 5,581,005,U.S. Pat. No. 5,559,261, U.S. Pat. No. 4,515,705, U.S. Pat. No.5,169,552, and U.S. Pat. No. 4,714,562.

All-purpose cleaners including bucket dilutable cleaners and toiletcleaners, bathroom cleaners, bath tissue, rug deodorizers, candles, roomdeodorizers, floor cleaners, disinfectants, window cleaners, garbagebags/trash can liners, moisture absorbers, household devices such aspaper towels and disposable wipes and moth balls/traps/cakes

Air Fresheners including room deodorizer and car deodorizer, scentedcandles, sprays, scented oil air freshener, Automatic spray airfreshener, and neutralizing gel beads.

Baby care products such as diaper rash cream/balm, baby powder, and babycare devices such as diapers, bibs and wipes.

Oral care products. Tooth care products (as an example of preparationsaccording to the invention used for oral care) generally include anabrasive system (abrasive or polishing agent), for example silicicacids, calcium carbonates, calcium phosphates, aluminum oxides and/orhydroxylapatites, surface-active substances, for example sodium laurylsulfate, sodium lauryl sarcosinate and/or cocamidopropylbetaine,humectants, for example glycerol and/or sorbitol, thickening agents, forexample carboxymethyl cellulose, polyethylene glycols, carrageenanand/or LAPONITE, sweeteners, for example saccharin, taste correctors forunpleasant taste sensations, taste correctors for further, normally notunpleasant taste sensations, taste-modulating substances (for exampleinositol phosphate, nucleotides such as guanosine monophosphate,adenosine monophosphate or other substances such as sodium glutamate or2-phenoxypropionic acid), cooling active ingredients, for examplementhol derivatives, (for example L-menthyllactate,L-menthylalkylcarbonates, menthone ketals, menthane carboxylic acidamides), 2,2,2-trialkylacetic acid amides (for example2,2-diisopropylpropionic acid methyl amide), icilin and icilinderivatives, stabilizers and active ingredients, for example sodiumfluoride, sodium monofluorophosphate, tin difluoride, quaternaryammonium fluorides, zinc citrate, zinc sulfate, tin pyrophosphate, tindichloride, mixtures of various pyrophosphates, triclosan,cetylpyridinium chloride, aluminum lactate, potassium citrate, potassiumnitrate, potassium chloride, strontium chloride, hydrogen peroxide,flavorings and/or sodium bicarbonate or taste correctors.

Tooth Paste. An exemplary formulation includes 40-55% calcium phosphate,0.8-1.2% carboxymethyl cellulose, 1.5-2.5% sodium lauryl sulfate, 20-30%glycerol, 0.1-0.3% saccharin, 1.0-2.5% flavor oil, water q.s. to 100%. Atypical procedure for preparing the formulation includes the steps of(i) mixing by a blender according to the foregoing formulation toprovide a toothpaste, and (ii) adding a composition of this inventionand blending the resultant mixture till homogeneous.

Other oral care products include, but are not limited to, tooth powders,ral rinses, tooth whiteners, and denture adhesives as well as heath caredevices such as dental floss, toothbrushes, and respirators.

Feminine hygiene products such as tampons, feminine napkins and wipes,and pantiliners.

Personal care products including cosmetic or pharmaceuticalpreparations, e.g., a “water-in-oil” (W/O) type emulsion, an“oil-in-water” (O/W) type emulsion or as multiple emulsions, for exampleof the water-in-oil-in-water (W/O/W) type, as a PIT emulsion, aPickering emulsion, a micro-emulsion or nano-emulsion; and emulsionswhich are particularly preferred are of the “oil-in-water” (O/W) type orwater-in-oil-in-water (W/O/W) type. More specifically, personalcleansers (bar soaps, body washes, and shower gels), in-showerconditioners, sunscreen and tattoo color protections (sprays, lotions,and sticks), insect repellants, hand sanitizers, antiinflammatory balms,ointments, and sprays, antibacterial ointments and creams, sensates,deodorants and antiperspirants including aerosol and pump sprayantiperspirant, stick antiperspirant, roll-on antiperspirant, emulsionspray antiperspirant, clear emulsion stick antiperspirant, soft solidantiperspirant, emulsion roll-on antiperspirant, clear emulsion stickantiperspirant, opaque emulsion stick antiperspirant, clear gelantiperspirant, clear stick deodorant, gel deodorant, spray deodorant,roll-on, and cream deordorant.

An exemplary formulation of a wax-based deodorant includes 10-20%parafin wax, 5-10% hydrocarbon wax, 10-15% white petrolatum, 2-4%acetylated lanolin alcohol, 4-8% diisopropyl adipate, 40-60% mineraloil, and preservative (as needed). The formulation is prepared by (i)mixing the above ingredients, (ii) heating the resultant composition to75° C. until melted, (iii) with stirring, adding 4% cryogenically groundpolymer containing a fragrance while maintaining the temperature 75° C.,and (iv) stirring the resulting mixture in order to ensure a uniformsuspension while a composition of this invention is added to theformulation.

An exemplary formulation of a Glycol/Soap Type Deodorant includes 60-70%Propylene Glycol, 5-10% Sodium Stearate, 20-30% Distilled Water, and0.01-0.5% 2,4,4-Trichloro-2′-Hydroxy Diphenyl Ether, manufactured by theCiba-Geigy Chemical Company and a Trademark of the Ciba-Geigy ChemicalCompany). The ingredients are combined and heated to 75° C. withstirring until the sodium stearate has dissolved. The resulting mixtureis cooled to 40° C. followed by addition of a composition of thisinvention.

Other personal care products include lotions (e.g., body lotion, faciallotion, and hand lotion, body powder and foot powder, toiletries, bodyspray, shave cream and male grooming products, bath soak, andexfoliating scrub as well as personal care devices such as facialtissues and cleansing wipes.

Hair care products include, but are not limited to, shampoos (liquid anddry powder), hair conditioners (rinse-out conditioners, leave-inconditioners, and cleansing conditioners), hair rinses, hair refreshers,hair perfumes, hair straightening products, hair styling products, hairfixative and styling aids, hair combing creams, hair wax, hair foam,hair gel, nonaerosol pump spray, hair bleaches, hair dyes, haircolorants, perming agents, and hair wipes.

Beauty care products include, but are not limited to, fine Fragrances,solid perfumes, lipstick/lip balm, make-up cleanser, skin care cosmeticssuch as foundation, pack, sunscreen, skin lotion, milky lotion, skincream, emollients, skin whitening and make-up cosmetics includingmanicure, mascara, eyeliner, eye shadow, liquid foundation, powderfoundation, lipstick and cheek rouge.

Compositions and methods for incorporating fragrance capsules intoalcoholic fine fragrances are described in U.S. Pat. No. 4,428,869.Alcoholic fine fragrances may contain the following 1-99% Ethanol, 0-99%water, 0.1-1% suspending aide including, but not limited to,hydroxypropyl cellulose, ethyl cellulose, silica, microcrystallinecellulose, carrageenan, propylene glycol alginate, methyl cellulose,sodium carboxymethyl cellulose or xanthan gum, and an optionalemulsifier or emollient.

Consumer goods packaging such as fragranced cartons, fragranced plasticbottles/boxes are also encompassed within the scope of this invention asare pet care products such as cat litter, Flea and tick treatmentproducts, Pet grooming products, pet shampoos, pet toys, pet treats, petchewables, pet training pags and pet carriers and crates.

The above-listed applications are all well known in the art. Forexample, fabric softener systems are described in U.S. Pat. No.6,335,315, U.S. Pat. No. 5,674,832, U.S. Pat. No. 5,759,990, U.S. Pat.No. 5,877,145, U.S. Pat. No. 5,574,179; U.S. Pat. No. 5,562,849, U.S.Pat. No. 5,545,350, U.S. Pat. No. 5,545,340, U.S. Pat. No. 5,411,671,U.S. Pat. No. 5,403,499, U.S. Pat. No. 5,288,417, U.S. Pat. No.4,767,547, and U.S. Pat. No. 4,424,134. Liquid laundry detergentsinclude those systems described in U.S. Pat. No. 5,929,022, U.S. Pat.No. 5,916,862, U.S. Pat. No. 5,731,278, U.S. Pat. No. 5,565,145, U.S.Pat. No. 5,470,507, U.S. Pat. No. 5,466,802, U.S. Pat. No. 5,460,752,U.S. Pat. No. 5,458,810, U.S. Pat. No. 5,458,809, U.S. Pat. No.5,288,431, U.S. Pat. No. 5,194,639, U.S. Pat. No. 4,968,451, U.S. Pat.No. 4,597,898, U.S. Pat. No. 4,561,998, U.S. Pat. No. 4,550,862, U.S.Pat. No. 4,537,707, U.S. Pat. No. 4,537,706, U.S. Pat. No. 4,515,705,U.S. Pat. No. 4,446,042, and U.S. Pat. No. 4,318,818. Liquid dishdetergents are described in U.S. Pat. No. 6,069,122 and U.S. Pat. No.5,990,065. Shampoo and conditioners that can employ the presentinvention include those described in U.S. Pat. No. 6,162,423, U.S. Pat.No. 5,968,286, U.S. Pat. No. 5,935,561, U.S. Pat. No. 5,932,203, U.S.Pat. No. 5,837,661, U.S. Pat. No. 5,776,443, U.S. Pat. No. 5,756,436,U.S. Pat. No. 5,661,118, U.S. Pat. No. 5,618,523, U.S. Pat. No.5,275,755, U.S. Pat. No. 5,085,857, U.S. Pat. No. 4,673,568, U.S. Pat.No. 4,387,090 and U.S. Pat. No. 4,705,681. Automatic Dish Detergents aredescribed in U.S. Pat. No. 6,020,294, U.S. Pat. No. 6,017,871, U.S. Pat.No. 5,968,881, U.S. Pat. No. 5,962,386, U.S. Pat. No. 5,939,373, U.S.Pat. No. 5,914,307, U.S. Pat. No. 5,902,781, U.S. Pat. No. 5,705,464,U.S. Pat. No. 5,703,034, U.S. Pat. No. 5,703,030, U.S. Pat. No.5,679,630, U.S. Pat. No. 5,597,936, U.S. Pat. No. 5,581,005, U.S. Pat.No. 5,559,261, U.S. Pat. No. 4,515,705, U.S. Pat. No. 5,169,552, andU.S. Pat. No. 4,714,562.

All parts, percentages and proportions refer to herein and in the claimsare by weight unless otherwise indicated.

The values and dimensions disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such value is intended to mean both therecited value and a functionally equivalent range surrounding thatvalue. For example, a value disclosed as “50%” is intended to mean“about 50%.”

The invention is described in greater detail by the followingnon-limiting examples. Without further elaboration, it is believed thatone skilled in the art can, based on the description herein, utilize thepresent invention to its fullest extent.

Example 1: Discovery of VOLUMINIS (Protein Modified with Cationic Group)as Efficient Deposition Aid

Composition 1: Polyurea capsule+VOLUMINIS 192.0 g of a fragrance Apple(International Flavors and Fragrance Inc., Union Beach, N.J.) wasweighed out and combined with 48.0 g of caprylic/capric triglyceride(NEOBEE), and 19.2 g of polymethylene polyphenylpolyisocyanate(LUPRANATE), to form the oil phase. In a separate beaker, 3 g ofnaphthalene sulfonate condensate (MORWET D-425) was dissolved in 316.2 gdistilled water to make the aqueous solution. This was then emulsifiedwith the previously prepared oil phase to form the fragrance emulsionunder high shearing (IKA-ULTRA TURRAX, T25 Basic) at 9500 rpm for threeminutes. The fragrance emulsion was heated to a 35° C. and 21.6 g of40.0% hexamethylene diamine was added under constant mixing with anoverhead mixer. After 15 minutes of stirring at 35° C., the capsuleslurry was cured at 55° C. for two hours. After two hours, the capsuleslurry was allowed to cool back down to room temperature under constantmixing.

Freshly prepared capsule slurry (83.8 g) was then mixed with 3.8 g ofVOLUMINIS-LQ-WD (Croda, Table 3) using an overhead mixer for 30 minutesat room temperature.

Comparison 1: Polyurea Caspule+CRODASONE. This comparative capsule wasprepared following the same procedure as Composition 1 except, 82.9 g offreshly prepared capsule slurry was mixed with 2.9 g of CRODASONEW-LQ-(WD) (Croda, Table 3) using an overhead mixer for 30 minutes atroom temperature.

Comparison 2: Polyurea Capsule+KERAVIS. This comparative capsule wasprepared following the same procedure as Composition 1 except, 84.0 g offreshly prepared capsule slurry was mixed with 4.0 g of KERAVIS-LQ-(WD)(Croda, Table 3) using an overhead mixer for 30 minutes at roomtemperature.

TABLE 3 Molecular Weight Description VOLUMINIS 50000Ethyltrimmoniumchloride methacrylate- wheat protein copolymer CRODASONE50000 Hydrolyzed wheat protein PG-propyl silantriol KERAVIS 1800Hydrolyzed vegetable protein PG-propyl silantriol

Fragrance Intensity in Shampoo.

The performance of Composition 1 and Comparisons 1-2 was evaluated inshampoo. More specifically, Composition 1 and Comparisons 1-2 were eachblended into a model shampoo (MAGICK Botanical). To the shampoo base wasadded 0.5% fragrance oil equivalent of the capsule slurries. The basewas subsequently mixed at high shear, 4000-6000 rpm for 1-2 minutes. Totwo bundle hair swatches (8 strands) that were wetted under water, withexcess water squeezed lightly, was added 2.0 g of the prepared hairshampoo base. After the hair was lathered, the hair swatches were rinsedunder a stream of water (38° C., 1 gal/min) for 45 seconds, excess waterfrom hair was removed. Hair swatches were line-dried for 24 hoursfollowed by sensory evaluation by a panel of judges. The fragranceintensity was rated on a scale ranging from 0 to 10 pre- andpost-brushing the hair swatches with a typical comb. A numerical valueof 5 indicated the hair swatches produced a strong intensity, while avalue of 10 indicated the hair swatches generated a very strong smell.The results are summarized in Table 4.

TABLE 4 Shampoo Performance (Intensity) Composition Pre-brush Post-brush1 1.4 4.4 Comparison 1 0.50 1.3 Comparison 2 1.1 1.6

It was surprisingly found that Composition 1 showed significantpost-brush benefits from shampoo. Based on knowledge of cationic-basematerials, performance has never been found at such a low molecularweight range. Furthermore, performance was only observed when cationicproperty was combined with the protein.

Fragrance Intensity in a Liquid Detergent Base.

The performance of Composition 1 and Comparisons 1-2 was also evaluatedin a liquid detergent base. More specifically, Composition 1 andComparisons 1-2 were each blended into a model un-fragrance liquiddetergent base at 0.5% fragrance oil equivalence. The resulting base wasapplied to a standard US washing machine protocol with towels asdescribed in U.S. Pat. No. 8,299,011. The towels were line-dried for 24hours followed by sensory evaluations by a panel of judges. Thefragrance intensity was rated on a scale ranging from 0 to 35 at pre-and post-rubbing the towel swatches. A numerical value of 15 indicatedthe towel producing a strong intensity, while 35 indicated the towelgenerated a very strong smell. The results are summarized in Table 5.

TABLE 5 Liquid Detergent (Intensity) Composition Pre-rub Post-rub 1 4.810.8 Comparison 1 2.6 4.2 Comparison 2 2.7 4.0

It was surprisingly found that Composition 1 showed significant post-rubbenefit from liquid detergent. Again, this was the first time to observesuch a high performance with low molecular weight cationic polymer.Further, performance was only observed when cationic moiety was presentwith the protein.

Example 2: Discovery of Efficient Use of CRODASONE (Protein Modifiedwith Silanetriol Group) as Deposition System when Post-Polymerized ViaHeat Treatement with Additional Deposition Aid

Composition 2: Polyurea Capsule+CRODASONE+Deposition Polymers+Heat.192.0 g of a fragrance Apple (International Flavors and Fragrance Inc.,Union Beach, N.J.) was weighed out and combined with 48.0 g ofcaprylic/capric triglyceride (NEOBEE), and 19.2 g of polymethylenepolyphenylpolyisocyanate (LUPRANATE), to form the oil phase. In aseparate beaker, 3 g of naphthalene sulfonate condensate (MORWET D-425)was dissolved in 244.3 g distilled water to make the aqueous solution.This was then emulsified with the previously prepared oil phase to formthe fragrance emulsion under high shearing (IKA-ULTRA TURRAX, T25 Basic)at 9500 rpm for three minutes. The fragrance emulsion was heated to 35°C. and 21.6 g of 40.0% hexamethylene diamine was added under constantmixing with an overhead mixer. After 15 minutes of stirring at 35° C.,20.8 g of CRODASONE W-LQ-(WD) (Croda) was added and the capsule slurrywas heated to 55° C., at which point 28.6 g of LUPAMIN 9095 (BASF) wasadded. After one hour of curing, 22.5 g of MERQUAT 100 (Lubrizol) wasadded and cured for additional 1 hour at 55° C., at which time thecapsule slurry was allowed to cool back down to room temperature underconstant mixing.

Comparison 3: Polyurea Capsule+CRODASONE+Deposition Polymers+No Heat. To0.81 g of COMPARISON 2 was mixed with 0.04 g of LUPAMIN followed by 0.03g of MERQUAT 100 (Luprizol) at room temperature and mixed with a spatulauntil a homogenous mixture was obtained.

Comparison 4: Polyurea Capsule+KERAVIS+Deposition Polymers+Heat. Thiscomparative capsule was prepared following the same procedure asComposition 1 except, 236.4 g of distilled water and 28.7 g ofKERAVIS-LQ-(WD) (Croda) was added.

Comparison 5: Polyurea Capsule+KERAVIS Deposition Polymers+No Heat. To0.82 g of COMPARISON 3 was mixed with 0.04 g of LUPAMIN followed by 0.03g of MERQUAT 100 (Luprizol) at room temperature using a spatula until ahomogenous mixture was obtained.

Fragrance Intensity in Shampoo.

The performance of Composition 2 and Comparisons 3-5 was evaluated inshampoo. More specifically, Composition 2 and Comparisons 3-5 were eachblended into a model shampoo (MAGICK Botanical). To the shampoo base wasadded 0.5% fragrance oil equivalent of the capsule slurries. The slurrywas mixed at high shear, 4000-6000 rpm for 1-2 minutes. To two bundlehair swatches (8 strands) that were wetted under water, with excesswater squeezed lightly, was added 2.0 g of the prepared hair shampoobase. After the hair was lathered, the hair swatches were rinsed under astream of water (38° C., 1 gal/min) for 45 seconds, excess water fromhair was removed. Hair swatches were line-dried for 24 hours followed bysensory evaluation by a panel of judges. The fragrance intensity wasrated on a scale ranging from 0 to 10 pre- and post-brushing the hairswatches with a typical comb. A numerical value of 5 indicated the hairswatches produced a strong intensity, while a value of 10 indicated thehair swatches generated a very strong smell. The results are summarizedin Table 6.

TABLE 6 Shampoo Performance (Intensity) Composition Pre-brush Post-brush2 1.4 3.6 Comparison 3 0.7 0.9 Comparison 4 0.7 1.3 Comparison 5 0.5 0.9

It was surprisingly found that Composition 2 showed significantpost-brush benefits from shampoo, when heating was used to inducepost-polymerization of the silane-triol group found in CRODASONE. It wasalso found that while a similar silane-triol group was present inKERAVIS, heat-induced post-polymerization did not help with increasingthe performance significantly. This may be attributed to the much lowermolecular weight of KERAVIS compared to CRODASONE. A higherconcentration of KERAVIS may increase the performance.

Example 3: Discovery of CRODASONE (Protein Modified with SilanetriolGroup) Heat Treatment with Additional Deposition Aid Showing EfficiencyAgainst Neutral Charged Capsules

Composition 3: Neutral Polyurea Capsule+CRODASONE+DepositionPolymers+Heat. This composition was prepared following the sameprocedure as Composition 2 except, 3 g of partially hydrolyzed polyvinylalcohol (MOWIOL 3-83-Kuraray) was used.

Comparison 6: Neutral Polyurea Capsule+CRODASONE+Deposition Polymer+NoHeat. This comparative capsule was prepared following the same procedureas Comparison 2 except 3 g of partially hydrolyzed polyvinyl alcohol(MOWIOL 3-83—Kuraray) was used. Then to 0.81 g of freshly preparedslurry was mixed with 0.04 g of LUPAMIN followed by 0.03 g of MERQUAT100 (Luprizol) at room temperature and using a spatula until homogenousmixture was obtained.

Comparison 7: Neutral Polyurea Capsule+KERAVIS+Deposition Polymer+Heat.This comparative capsule was prepared following the same procedure asCOMPARISON 4 except, 3 g of partially hydrolyzed polyvinyl alcohol(MOWIOL 3-83—Kuraray) was used.

Comparison 8: Neutral Polyurea Capsule+KERAVIS+Deposition Polymer+NoHeat. This comparative capsule was prepared following the same procedureas Comparison 3 except, 3 g of partially hydrolyzed polyvinyl alcohol(MOWIOL 3-83—Kuraray) was used. Then to 0.82 g of freshly preparedslurry was mixed with 0.04 g of LUPAMIN followed by 0.03 g of MERQUAT100 (Luprizol) at room temperature and using a spatula until homogenousmixture was obtained.

Comparison 9: Neutral Polyurea Capsule+VOLUMINIS+No Heat. Thiscomparative capsule was prepared following the same procedure asComposition 1 except, 3 g of partially hydrolyzed polyvinyl alcohol(MOWIOL 3-83—Kuraray) was used.

Comparison 10: Neutral Polyurea Capsule+VOLUMINIS+Deposition Polymer+NoHeat. To 0.82 g of Comparative 9 was mixed with 0.04 g of LUPAMINfollowed by 0.03 g of MERQUAT 100 (Luprizol) at room temperature using aspatula until homogenous mixture was obtained.

Comparison 11: Polyurea Capsule. This comparative capsule was preparedfollowing the same procedure as Composition 1 except, no VOLUMINIS-LQ-WD(Croda) was added.

Comparison 12: Neutral Polyurea Capsule. This comparative capsule wasprepared following the same procedure as Comparison 9 except, noVOLUMINIS-LQ-WD (Croda) was added.

Fragrance Intensity in Shampoo.

The performance of Composition 3 and Comparisons 6-10 was evaluated inshampoo. More specifically Composition 3 and Comparisons 6-10 were eachblended into a model shampoo (MAGICK Botanical). To the shampoo base wasadded 0.5% fragrance oil equivalent of the capsule slurries. Theslurries were mixed at high shear, 4000-6000 rpm for 1-2 minutes. To twobundle hair swatches (8 strands) that were wetted under water, withexcess water squeezed lightly, was added 2.0 g of the prepared hairshampoo base. After the hair was lathered, the hair swatches were rinsedunder a stream of water (38° C., 1 gal/min) for 45 seconds, excess waterfrom hair was removed. Hair swatches were line-dried for 24 hoursfollowed by sensory evaluation by a panel of judges. The fragranceintensity was rated on a scale ranging from 0 to 10 pre- andpost-brushing the hair swatches with a typical comb. A numerical valueof 5 indicated the hair swatches produced a strong intensity, while avalue of 10 indicated the hair swatches generated a very strong smell.The results are summarized in Table 7.

TABLE 7 Shampoo Performance (Intensity) Composition Pre-brush Post-brush3 1.7 3.9 Comparison 6 0.3 0.5 Comparison 7 0.8 2.1 Comparison 8 0.6 1.2Comparison 9 0.5 0.9 Comparison 10 0.3 0.6

It was surprisingly found that Composition 3 showed significantpost-brush benefits from shampoo, when heating was used to induce thepost-polymerization process of the silane-triol group found inCRODASONE, while the capsule charged was more neutral. As indicated inTable 8, capsule with MORWET D-425 as a dispersant had a higher negativesurface charge. Whereas when the dispersant was replaced with MOWIOL3-83, the capsule was more neutral. With more negative charge, betterinteraction was usually observed with cationic materials thereforebetter performance. The post-polymerization step of CRODASONE may haveincreased the interaction process of the cationic material to the moreneutral surface. While some benefits were observed using KERAVIS, thefragrance intensity was not as high. This again may be attributed to themuch lower molecular weight of KERAVIS compared to CRODASONE. Thus, ahigher concentration of KERAVIS may increase the performance.

TABLE 8 Dispersant Capsule Surface Charge (mV) Comparison 11 MORWETD-425 −56.6 Comparison 12 MOWIOL 3-83 −6.3

What is claimed is:
 1. A microcapsule composition comprising a pluralityof microcapsules each containing a polymeric wall and an active materialencapsulated within the polymeric wall, wherein the polymeric wall iscoated with a deposition protein.
 2. The microcapsule composition ofclaim 1, wherein the deposition protein is a cationically modifiedprotein, a protein-silanol copolymer, a protein-silane, aprotein-siloxane copolymer, or a combination thereof.
 3. Themicrocapsule composition of claim 2, wherein the cationically modifiedprotein is a protein-acrylate copolymer comprising at least onenitrogen-containing acrylic moiety.
 4. The microcapsule composition ofclaim 3, wherein the nitrogen-containing acrylic moiety comprises atertiary or quaternary amine group.
 5. The microcapsule composition ofclaim 2, wherein the deposition protein has the structure of Formula Ior Formula II:

wherein R is a protein residue; R¹ is a protein cross-linker group; R²and R³ are each independently hydrogen, hydroxyl, halo, C₁-C₆ alkyl, orC₁-C₆ alkoxy; and n is 1 to
 100. 6. The microcapsule composition ofclaim 1, wherein the deposition protein is a modified vegetable protein,wheat protein, marine collagen protein, keratin protein, silk protein,or milk protein.
 7. The microcapsule composition of claim 1, wherein thedeposition protein has a molecular weight in the range of 1000 to500,000.
 8. The microcapsule composition of claim 1, wherein the activematerial is a fragrance, pro-fragrance, flavor, malodor counteractiveagent, anti-inflammatory agent, anesthetic, analgesic, anti-viral agent,anti-infectious agent, anti-acne agent, skin lightening agent, insectrepellant, emollient, skin moisturizing agent, vitamin or derivativethereof, nanometer to micron size inorganic solid, polymeric orelastomeric particle, or combination thereof.
 9. The microcapsulecomposition of claim 1, wherein the polymeric wall comprisespolyacrylate, polyurea, polyurethane, polyacrylamide,poly(acrylate-co-acrylamide), starch, silica, gelatin and gum Arabic,poly(melamine-formaldehyde), poly(urea-formaldehyde), or a combinationthereof.
 10. The microcapsule composition of claim 1, further comprisinga second deposition aid.
 11. A method for preparing the microcapsulecomposition of claim 1, comprising: (a) providing a microcapsule slurryhaving a plurality of microcapsules each containing a polymeric wall andan active material encapsulated within the polymeric wall; and (b)curing the microcapsules and coating each of the microcapsules with adeposition protein.
 12. The method of claim 11, wherein themicrocapsules are coated with the deposition protein at a temperaturebetween 0 to 250° C. before, during or after curing the microcapsules.13. The method of claim 11, further comprising step (c) adding atransglutaminase after step (b) to cross-link the deposition protein.14. The method of claim 11, further comprising step (d) adding a seconddeposition aid after step (b).
 15. The method of claim 11, wherein thedeposition protein is a protein-silanol copolymer, a protein-silanecopolymer, a protein-siloxane copolymer, or a cationically modifiedprotein.
 16. The method of claim 15, wherein the cationically modifiedprotein is a protein-acrylate copolymer having a nitrogen-containingacrylic moiety.
 17. The method of claim 16, wherein thenitrogen-containing acrylic moiety comprises a tertiary or quaternaryamine group.
 18. The method of claim 15, wherein the deposition proteinis a protein-silanol copolymer, a protein-silane copolymer, aprotein-siloxane copolymer, or a combination thereof, and themicrocapsules are coated at a temperature between 35 to 75° C. before,during or after curing the microcapsules.
 19. The method of claim 11,further comprising step (e) adding an alkoxysilane after step (b) tocross-link the deposition protein.
 20. The method of claim 11, whereinthe plurality of microcapsules are prepared by cross-linking apolyisocyanate with an activation agent selected from the groupconsisting of an amine cross-linker, an alcohol cross-linker, an epoxycross-linker, an acrylate cross-linker, a hybrid cross-linker, and acombination thereof.
 21. The method of claim 20, wherein the aminecross-linker contains two or more amine groups, the alcohol cross-linkercontains two or more hydroxyl groups, the epoxy cross-linker containstwo or more epoxy groups, the acrylate cross-linker contains two or moreacrylate groups, and the hybrid cross-linker contains one or more aminegroups and one or more hydroxyl groups.
 22. A consumer productcomprising the microcapsule composition of claim
 1. 23. The consumerproduct of claim 22, further comprising one or more differentmicrocapsules, free active material, or a combination thereof.
 24. Theconsumer product of claim 22, wherein the consumer product is a shampoo,hair conditioner, body wash, detergent, softener, bar soap, scentbooster, or hard surface cleaner.